U.S. patent number 10,479,940 [Application Number 15/568,485] was granted by the patent office on 2019-11-19 for liquid crystal composition and liquid crystal display device.
This patent grant is currently assigned to JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. The grantee listed for this patent is JNC CORPORATION, JNC PETROCHEMICAL CORPORATION. Invention is credited to Naoko Matsuda, Masayuki Saito.
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United States Patent |
10,479,940 |
Matsuda , et al. |
November 19, 2019 |
Liquid crystal composition and liquid crystal display device
Abstract
A liquid crystal compound having positive dielectric anisotropy
is provided and contains a compound represented by formula (1) as a
first component, a compound represented by formula (2) as a second
component, a polar compound as a first additive and a polymerizable
compound as a second additive. ##STR00001## In formula (1),
R.sup.1a is alkyl having 1 to 12 carbons, or the like; ring Q and
ring S are independently 1,4-cyclohexylene, 1,4-phenylene or the
like; Z.sup.1a and Z.sup.2a are independently a single bond or the
like; X.sup.1a and X.sup.2a are independently hydrogen or fluorine;
Y.sup.1a is fluorine, chlorine, alkyl having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine, or
the like; q is 1, 2, 3 or 4; s is 0, 1, 2 or 3; and a sum of q and
s is 4 or less.
Inventors: |
Matsuda; Naoko (Chiba,
JP), Saito; Masayuki (Chiba, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
JNC CORPORATION
JNC PETROCHEMICAL CORPORATION |
Tokyo
Tokyo |
N/A
N/A |
JP
JP |
|
|
Assignee: |
JNC CORPORATION (Tokyo,
JP)
JNC PETROCHEMICAL CORPORATION (Tokyo, JP)
|
Family
ID: |
57144412 |
Appl.
No.: |
15/568,485 |
Filed: |
March 31, 2016 |
PCT
Filed: |
March 31, 2016 |
PCT No.: |
PCT/JP2016/060659 |
371(c)(1),(2),(4) Date: |
October 23, 2017 |
PCT
Pub. No.: |
WO2016/170948 |
PCT
Pub. Date: |
October 27, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20180105746 A1 |
Apr 19, 2018 |
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Foreign Application Priority Data
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Apr 23, 2015 [JP] |
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2015-088074 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09K
19/42 (20130101); C09K 19/3402 (20130101); C09K
19/34 (20130101); C09K 19/54 (20130101); C09K
19/3003 (20130101); C09K 19/20 (20130101); C09K
19/44 (20130101); C09K 19/32 (20130101); C09K
19/12 (20130101); G02F 1/1333 (20130101); C09K
19/38 (20130101); C09K 19/3066 (20130101); C09K
19/30 (20130101); C09K 2019/301 (20130101); C09K
2019/122 (20130101); C09K 2019/3425 (20130101); C09K
2019/0466 (20130101); C09K 2019/3004 (20130101); C09K
2019/3422 (20130101); C09K 2019/0448 (20130101) |
Current International
Class: |
G02F
1/1334 (20060101); C09K 19/38 (20060101); C09K
19/42 (20060101); C09K 19/54 (20060101); C09K
19/44 (20060101); G02F 1/1333 (20060101); C09K
19/20 (20060101); C09K 19/32 (20060101); C09K
19/30 (20060101); C09K 19/34 (20060101); C09K
19/12 (20060101); C09K 19/04 (20060101) |
Field of
Search: |
;252/299.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2013-144796 |
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Jul 2013 |
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JP |
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2013-541028 |
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Nov 2013 |
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JP |
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2013-543526 |
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Dec 2013 |
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JP |
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2014-047354 |
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Mar 2014 |
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JP |
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2014-097938 |
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May 2014 |
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JP |
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2014-513150 |
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May 2014 |
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JP |
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2014-196265 |
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Oct 2014 |
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JP |
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201202400 |
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Jan 2012 |
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TW |
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2012038026 |
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Mar 2012 |
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WO |
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2012104008 |
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Aug 2012 |
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WO |
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2013004372 |
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Jan 2013 |
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WO |
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2014090362 |
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Jun 2014 |
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WO |
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2014094959 |
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Jun 2014 |
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WO |
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2015004947 |
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Jan 2015 |
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WO |
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Other References
"International Search Report (Form PCT/ISA/210)", dated Jun. 21,
2016, with English translation thereof, pp. 1-5. cited by applicant
.
"Office Action of Taiwan Counterpart Application," dated May 8,
2019, with English translation thereof, p. 1-p. 16. cited by
applicant.
|
Primary Examiner: Visconti; Geraldina
Attorney, Agent or Firm: JCIPRNET
Claims
What is claimed is:
1. A liquid crystal composition that has positive dielectric
anisotropy, and contains at least one compound selected from the
group of compounds represented by formula (1) as a first component,
a compound represented by formula (2) as a second component, at
least one polar compound as a first additive and at least one
polymerizable compound as a second additive: ##STR00071## wherein,
in formula (1), R.sup.1a is alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring Q
and ring S are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z.sup.1a and
Z.sup.2a are independently a single bond, --CH.sub.2CH.sub.2--,
--CH.dbd.CH--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OCO--,
--CF.sub.2O-- or --OCF.sub.2--; X.sup.1a and X.sup.2a are
independently hydrogen or fluorine; Y.sup.1a is fluorine, chlorine,
alkyl having 1 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine, or
alkenyloxy having 2 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine; q is 1, 2, 3 or 4; s is 0, 1, 2
or 3; and a sum of q and s is 4 or less.
2. The liquid crystal composition according to claim 1, containing
at least one compound selected from the group of compounds
represented by formula (1-1) to formula (1-14) as the first
component: ##STR00072## ##STR00073## wherein, in formula (1-1) to
formula (1-14), R.sup.1a is alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons; X.sup.1a,
X.sup.2a, X.sup.3a, X.sup.4a, X.sup.5a, X.sup.6a, X.sup.7a,
X.sup.8a, X.sup.9a, X.sup.10a, X.sup.11a, X.sup.12a, X.sup.13a and
X.sup.14a are independently hydrogen or fluorine; and Y.sup.1a is
fluorine, chlorine, alkyl having 1 to 12 carbons in which at least
one hydrogen is replaced by fluorine or chlorine, alkoxy having 1
to 12 carbons in which at least one hydrogen is replaced by
fluorine or chlorine, or alkenyloxy having 2 to 12 carbons in which
at least one hydrogen is replaced by fluorine or chlorine.
3. The liquid crystal composition according to claim 1, wherein a
proportion of the first component is in the range of 5% by weight
to 55% by weight, and a proportion of the second component is in
the range of 5% by weight to 50% by weight.
4. The liquid crystal composition according to claim 1, further
containing at least one compound selected from the group of
compounds represented by formula (3) as a third component:
##STR00074## wherein, in formula (3), R.sup.1a and R.sup.4a are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12
carbons in which at least one hydrogen is replaced by fluorine or
chlorine; ring U and ring V are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; Z.sup.1a is a single bond,
--CH.sub.2CH.sub.2--, --COO-- or --OCO--; u is 1, 2 or 3; in which,
when u is 1, ring V is 1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene.
5. The liquid crystal composition according to claim 1, further
containing at least one compound selected from the group of
compounds represented by formula (4): ##STR00075## wherein, in
formula (4), R.sup.5a is alkyl having 1 to 12 carbons, alkoxy
having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring W is
1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene,
2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene,
pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or
tetrahydropyran-2,5-diyl; Z.sup.4a is a single bond,
--CH.sub.2CH.sub.2--, --COO-- or --OCO--; X.sup.15a and X.sup.16a
are independently hydrogen or fluorine; Y.sup.2a is fluorine,
chlorine, alkyl having 1 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12
carbons in which at least one hydrogen is replaced by fluorine or
chlorine, or alkenyloxy having 2 to 12 carbons in which at least
one hydrogen is replaced by fluorine or chlorine; and w is 1, 2, 3
or 4.
6. The liquid crystal composition according to claim 1, containing
at least one compound selected from the group of compounds
represented by formula (5): ##STR00076## wherein, in formula (5),
R.sup.6a and R.sup.7a are independently alkyl having 1 to 12
carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12
carbons or alkenyloxy having 2 to 12 carbons; ring D and ring F are
independently 1,4-cyclohexylene, 1,4-cyclohexenylene,
1,4-phenylene, 1,4-phenylene in which at least one hydrogen is
replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl; ring
E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene,
2,3-difluoro-5-methyl-1,4-phenylene,
3,4,5-trifluoronaphthalene-2,6-diyl or
7,8-difluorochroman-2,6-diyl; Z.sup.5a and Z.sup.6a are
independently a single bond, --CH.sub.2CH.sub.2--, --COO--,
--OCO--, --CH.sub.2O-- or --OCH.sub.2--; e is 1, 2 or 3, and f is 0
or 1; and a sum of e and f is 3 or less.
7. The liquid crystal composition according to claim 1, wherein the
first additive is a polar compound having a polar group containing
a hetero atom selected from nitrogen, oxygen, sulfur and
phosphorus.
8. The liquid crystal composition according to claim 1, containing
at least one polar compound selected from the group of compounds
represented by formula (6) and formula (7) as the first additive:
MES-R.sup.5 (6) (R.sup.4).sub.g--R.sup.5 (7) wherein, in formula
(6), MES is a mesogen group having at least one ring; in formula
(7), R.sup.4 is alkyl having 4 to 20 carbons, and in the alkyl, at
least one piece of --CH.sub.2-- may be replaced by --CH.dbd.CH--,
--CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or cycloalkylene having
3 to 8 carbons, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine; and in formula (6) and formula
(7), R.sup.5 is a polar group having at least one of an oxygen atom
having an OH structure, a sulfur atom having an SH structure, and a
nitrogen atom having a primary, secondary or tertiary amine
structure; and g is 1 or 2.
9. The liquid crystal composition according to claim 8, containing
at least one compound selected from the group of compounds
represented by formula (6-1) as the first additive: ##STR00077##
wherein, in formula (6-1), ring G and ring I are independently an
aromatic group having 6 to 25 carbons, a heteroaromatic group
having 5 to 25 carbons, an alicyclic group having 3 to 25 carbons
or a heteroalicyclic group having 4 to 25 carbons, and the groups
may be a condensed ring, and in the groups, at least one hydrogen
may be replaced by group T, in which group T is --OH,
--(CH.sub.2).sub.i--OH, halogen, --CN, --NO.sub.2, --NCO, --NCS,
--OCN, --SCN, --C(.dbd.O)N(R.sup.0).sub.2, --C(.dbd.O)R.sup.0,
--N(R.sup.0).sub.2, --(CH.sub.2).sub.i--N(R.sup.0).sub.2, aryl
having 6 to 20 carbons, heteroaryl having 6 to 20 carbons, alkyl
having 1 to 25 carbons, alkoxy having 1 to 25 carbons,
alkylcarbonyl having 2 to 25 carbons, alkoxycarbonyl having 2 to 25
carbons, alkylcarbonyloxy having 2 to 25 carbons or
alkoxycarbonyloxy having 2 to 25 carbons, and in the groups, at
least one hydrogen may be replaced by fluorine or chlorine, in
which R.sup.0 is hydrogen or alkyl having 1 to 12 carbons, and i is
1, 2, 3 or 4; Z.sup.5 is --O--, --S--, --CO--, --CO--O--, --OCO--,
--O--CO--O--, --OCH.sub.2--, --CH.sub.2O--, --SCH.sub.2--,
--CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--, --CF.sub.2S--,
--SCF.sub.2--, --(CH.sub.2).sub.i--, --CF.sub.2CH.sub.2--,
--CH.sub.2CF.sub.2--, --(CF.sub.2).sub.i--, --CH.dbd.CH--,
--CF.dbd.CF, --C.ident.C--, --CH.dbd.CH--COO--, --OCO--CH.dbd.CH--,
--C(R.sup.0).sub.2 or a single bond, in which R.sup.0 is hydrogen
or alkyl having 1 to 12 carbons, and i is 1, 2, 3 or 4; R.sup.5 is
alkyl having 1 to 25 carbons, and in the alkyl, at least one piece
of --CH.sub.2-- may be replaced by --NR.sup.0--, --O--, --S--,
--CO--, --COO--, --OCO--, --OCOO-- or cycloalkylene having 3 to 8
carbons, in which R.sup.0 is hydrogen or alkyl having 1 to 12
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.5 has at least one
of an oxygen atom having an OH structure, a sulfur atom having an
SH structure, and a nitrogen atom having a primary, secondary or
tertiary amine structure; R.sup.6 is hydrogen, halogen and alkyl
having 1 to 25 carbons, and in the alkyl, at least one piece of
--CH.sub.2-- may be replaced by --NR.sup.0--, --O--, --S--, --CO--,
--CO--O--, --O--CO--, --O--CO--O-- or cycloalkylene having 3 to 8
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and in the groups, at least
hydrogen may be replaced by fluorine or chlorine, in which R.sup.0
is hydrogen or alkyl having 1 to 12 carbons; and his 0, 1, 2, 3, 4
or 5.
10. The liquid crystal composition according to claim 8, further
containing at least one polar compound selected from the group of
compounds represented by formula (7-1) as the first additive:
R.sup.4--R.sup.5 (7-1) wherein, in formula (7-1), R.sup.4 is alkyl
having 4 to 20 carbons, and in the alkyl, at least one piece of
--CH.sub.2-- may be replaced by --CH.dbd.CH--, --CF.dbd.CH--,
--CH.dbd.CF--, --C.ident.C-- or cycloalkylene having 3 to 8
carbons, and in the groups, at least one hydrogen may be replaced
by fluorine or chlorine; R.sup.5 is alkyl having 1 to 25 carbons,
and in the alkyl, at least one piece of --CH.sub.2-- may be
replaced by --NR.sup.0--, --O--, --S--, --CO--, --COO--, --OCO--,
--OCOO-- or cycloalkylene having 3 to 8 carbons, in which R.sup.0
is hydrogen or alkyl having 1 to 12 carbons, and at least one
tertiary carbon (>CH--) may be replaced by nitrogen (>N--),
and at least one hydrogen may be replaced by fluorine or chlorine,
in which R.sup.5 has at least one of an oxygen atom having an OH
structure, a sulfur atom having an SH structure, and a nitrogen
atom having a primary, secondary or tertiary amine structure.
11. The liquid crystal composition according to claim 8, wherein,
in formula (6) and formula (7), R.sup.5 is a group represented by
any one of formula (A1) to formula (A4): ##STR00078## wherein, in
formula (A1) to formula (A4), Sp.sup.4, Sp.sup.6 and Sp.sup.7 are
independently a single bond or a group (-Sp''-X''--), in which Sp''
is alkylene having 1 to 20 carbons, and in the alkylene, at least
one piece of --CH.sub.2-- may be replaced by --O--, --S--, --NH--,
--N(R.sup.0)--, --CO--, --CO--O--, --O--CO--, --O--CO--O--,
--S--CO--, --CO--S--, --N(R.sup.0)--CO--O--, --O--CO--N(R.sup.0)--,
--N(R.sup.0)--CO--N(R.sup.0)--, --CH.dbd.CH-- or --C.ident.C--, and
in the groups, at least one hydrogen may be replaced by fluorine,
chlorine or --CN, and X'' is --O--, --S--, --CO--, --CO--O--,
--O--CO--, --O--CO--O--, --CO--N(R.sup.0)--, --N(R.sup.0)--CO--,
--N(R.sup.0)--CO--N(R.sup.0)--, --OCH.sub.2--, --CH.sub.2O--,
--SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--,
--CF.sub.2S--, --SCF.sub.2--, --CF.sub.2CH.sub.2--,
--CH.sub.2CF.sub.2--, --CF.sub.2CF.sub.2--, --N.dbd.CH--,
--N.dbd.N--, --CH--CR.sup.0--, --CY.sup.2.dbd.CY.sup.3--,
--CH.dbd.CH--CO--O--, --O--CO--CH.dbd.CH-- or a single bond, in
which R.sup.0 is hydrogen or alkyl having 1 to 12 carbons, and
Y.sup.2 and Y.sup.3 are independently hydrogen, fluorine, chlorine
or --CN; Sp.sup.y is >CH--, >CR.sup.11--, >N-- or
>C<; X.sup.3 is --OH, --OR.sup.11, --COOH, --NH.sub.2,
--NHR.sup.11, --N(R.sup.11).sub.2, --SH, --SR.sup.11, ##STR00079##
in which R.sup.0 is hydrogen or alkyl having 1 to 12 carbons;
X.sup.4 is --O--, --CO--, --NH--, --NR.sup.11--, --S-- or a single
bond; Z.sup.6 is alkylene having 1 to 15 carbons, an alicyclic
group having 5 or 6 carbons or a combination thereof, and in the
groups, at least one hydrogen may be replaced by --OH, --OR.sup.11,
--COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2, fluorine or
chlorine, in which R.sup.11 is alkyl having 1 to 15 carbons, and in
the alkyl, at least one piece of --CH.sub.2-- may be replaced by
--C.ident.C--, --CH.dbd.CH--, --COO--, --OCO--, --CO-- or --O--,
and in the groups, at least one hydrogen may be replaced by
fluorine or chlorine; ring J is an aromatic group having 6 to 25
carbons or an alicyclic group having 3 to 25 carbons, and the
groups may be a condensed ring, and in the groups, one to three
hydrogens may be replaced by R.sup.L; R.sup.L is --OH,
--(CH.sub.2).sub.i--OH, fluorine, chlorine, --CN, --NO.sub.2,
--NCO, --NCS, --OCN, --SCN, --C(.dbd.O)N(R.sup.0).sub.2,
--C(.dbd.O)R.sup.0, --N(R.sup.0).sub.2,
--(CH.sub.2).sub.i--N(R.sup.0).sub.2, --SH, --SR.sup.0, aryl having
6 to 20 carbons, heteroaryl having 6 to 20 carbons, alkyl having 1
to 25 carbons, alkoxy having 1 to 25 carbons, alkylcarbonyl having
2 to 25 carbons, alkoxycarbonyl having 2 to 25 carbons,
alkylcarbonyloxy having 2 to 25 carbons or alkoxycarbonyloxy having
2 to 25 carbons, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.0 is hydrogen or
alkyl having 1 to 12 carbons, and i is 1, 2, 3 or 4; j is 0, 1, 2
or 3; and k is 2, 3, 4 or 5.
12. The liquid crystal composition according to claim 8, wherein
the first additive is at least one compound selected from the group
of compounds represented by formula (6-1-1) to formula (6-1-4):
##STR00080## wherein, in formula (6-1-1) to formula (6-1-4), ring G
and ring I are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 2-fluoro-1,3-phenylene,
2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene,
2-trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene or
2,3,5,6-tetrafluoro-1,4-phenylene; ring J is cyclohexyl or phenyl;
Z.sup.6 is a single bond, --CH.sub.2CH.sub.2--, --COO-- or --OCO--;
Z.sup.7 is a single bond, alkylene having 1 to 15 carbons, an
alicyclic group having 5 or 6 carbons or a combination thereof, and
in the groups, at least one hydrogen may be replaced by --OH,
--OR.sup.11, --COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2,
fluorine or chlorine, and R.sup.11 is alkyl having 1 to 15 carbons,
and in the alkyl, at least one piece of --CH.sub.2-- may be
replaced by --C.ident.C--, --CH.dbd.CH--, --COO--, --OCO--, --CO--,
--O-- or --NH--, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine; Sp.sup.4 is a single bond,
--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2--, --CH.sub.2O--
or --OCH.sub.2--; Sp.sup.7 is a single bond or alkylene having 1 to
5 carbons, and in the alkylene, --CH.sub.2-- may be replaced by
--O-- or --NH--; R.sup.7 is alkyl having 1 to 8 carbons or
fluorine; h is 0, 1, 2, 3, 4 or 5; X.sup.3 is --OH, --COOH, --SH,
--OCH.sub.3 or --NH.sub.2; and X.sup.4 is a single bond or
--O--.
13. The liquid crystal composition according to claim 8, wherein
the first additive is at least one compound selected from the group
of compounds represented by formula (7-1-1) to formula (7-1-29):
##STR00081## ##STR00082## wherein, in formula (7-1-1) to formula
(7-1-29), R.sup.4 is alkyl having 4 to 20 carbons, and in the
alkyl, at least one piece of --CH.sub.2-- may be replaced by
--CH.dbd.CH--, --CF.dbd.CH--, --CH.dbd.CF--, --C.ident.-- or
cycloalkylene having 3 to 8 carbons, and in the groups, at least
one hydrogen may be replaced by fluorine or chlorine.
14. The liquid crystal composition according to claim 8, wherein a
proportion of the first additive is 10% by weight or less.
15. The liquid crystal composition according to claim 1, containing
at least one polymerizable compound selected from the group of
compounds represented by formula (8) as the second additive:
##STR00083## wherein, in formula (8), ring A and ring C are
independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl,
2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl
or pyridine-2-yl, and in the rings, at least one hydrogen may be
replaced by fluorine, chlorine, alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine;
ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,
naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl,
naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl,
naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl,
naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl,
1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and
in the rings, at least one hydrogen may be replaced by fluorine,
chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons, or alkyl having 1 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine; Z.sup.1 and Z.sup.2
are independently a single bond or alkylene having 1 to 10 carbons,
and in the alkylene, at least one piece of --CH.sub.2-- may be
replaced by --O--, --CO--, --COO-- or --OCO--, and at least one
piece of --CH.sub.2CH.sub.2-- may be replaced by --CH.dbd.CH--,
--C(CH.sub.3).dbd.CH--, --CH.dbd.C(CH.sub.3)-- or
--C(CH.sub.3).dbd.C(CH.sub.3)--, and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine; P.sup.1, P.sup.2
and P.sup.3 are a polymerizable group; Sp.sup.1, Sp.sup.2 and
Sp.sup.3 are independently a single bond or alkylene 1 to 10
carbons, and in the alkylene, at least one piece of --CH.sub.2--
may be replaced by --O--, --COO--, --OCO-- or --OCOO--, and at
least one piece of --CH.sub.2CH.sub.2-- may be replaced by
--CH.dbd.CH-- or --C.ident.C--, and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine; a is 0, 1 or 2;
and b, c and d are independently 0, 1, 2, 3 or 4.
16. The liquid crystal composition according to claim 15, wherein,
in formula (8), P.sup.1, P.sup.2 and P.sup.3 are independently a
polymerizable group selected from the group of groups represented
by formula (P-1) to formula (P-5): ##STR00084## wherein, in formula
(P-1) to formula (P-5), M.sup.1, M.sup.2 and M.sup.3 are
independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or
alkyl having 1 to 5 carbons in which at least one hydrogen is
replaced by fluorine or chlorine.
17. The liquid crystal composition according to claim 15, wherein
the second additive is at least one polymerizable compound selected
from the group of compounds represented by formula (8-1) to formula
(8-28): ##STR00085## ##STR00086## ##STR00087## wherein, in formula
(8-1) to formula (8-28), P.sup.1, P.sup.2 and P.sup.3 are
independently a polymerizable group selected from the group of
groups represented by formula (P-1) to formula (P-3), in which
M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine,
alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in
which at least one hydrogen is replaced by fluorine or chlorine;
##STR00088## wherein, Sp.sup.1, Sp.sup.2 and Sp.sup.a are
independently a single bond or alkylene having 1 to 10 carbons, and
in the alkylene, at least one piece of --CH.sub.2-- may be replaced
by --O--, --OCO--, --OCO-- or --OCOO--, and at least one piece of
--CH.sub.2CH.sub.2-- may be replaced by --CH.dbd.CH-- or
--C.ident.C--, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine.
18. The liquid crystal composition according to claim 15, wherein a
proportion of the second additive is in the range of 0.03% by
weight to 10% by weight based on the weight of the liquid crystal
composition.
19. A polymer sustained alignment mode liquid crystal display
device, wherein the liquid crystal display device includes the
liquid crystal composition according to claim 1, or a polymerizable
compound in the liquid crystal composition is polymerized.
20. A polymer sustained alignment mode liquid crystal display
device having no alignment film, wherein the liquid crystal display
device includes the liquid crystal composition according to claim
1, or a polymerizable compound in the liquid crystal composition is
polymerized.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application is a 371 application of International PCT
application serial no. PCT/JP2016/060659, filed on Mar. 31, 2016,
which claims the priority benefit of Japan application no.
2015-088074, filed on Apr. 23, 2015. The entirety of each of the
abovementioned patent applications is hereby incorporated by
reference herein and made a part of this specification.
TECHNICAL FIELD
The invention relates to a liquid crystal composition, a liquid
crystal display device including the composition, and so forth. In
particular, the invention relates to a liquid crystal composition
that has positive dielectric anisotropy, contains a polar compound
and a polymerizable compound (or a polymer thereof), and can
achieve vertical alignment of liquid crystal molecules by action of
the above compounds, and a liquid crystal display device.
BACKGROUND ART
In a liquid crystal display device, a classification based on an
operating mode for liquid crystal molecules includes a phase change
(PC) mode, a twisted nematic (TN) mode, a super twisted nematic
(STN) mode, an electrically controlled birefringence (ECB) mode, an
optically compensated bend (OCB) mode, an in-plane switching (IPS)
mode, a vertical alignment (VA) mode, a fringe field switching
(FFS) mode and a field-induced photo-reactive alignment (FPA) mode.
A classification based on a driving mode in the device includes a
passive matrix (PM) and an active matrix (AM). The PM is classified
into static, multiplex and so forth, and the AM is classified into
a thin film transistor (TFT), a metal insulator metal (MIM) and so
forth. The TFT is further classified into amorphous silicon and
polycrystal silicon. The latter is classified into a high
temperature type and a low temperature type based on a production
process. A classification based on a light source includes a
reflective type utilizing natural light, a transmissive type
utilizing backlight and a transflective type utilizing both the
natural light and the backlight.
The liquid crystal display device includes a liquid crystal
composition having a nematic phase. The composition has suitable
characteristics. An AM device having good characteristics can be
obtained by improving characteristics of the composition. Table 1
below summarizes a relationship in two characteristics. The
characteristics of the composition will be further described based
on a commercially available AM device. A temperature range of the
nematic phase relates to a temperature range in which the device
can be used. A preferred maximum temperature of the nematic phase
is about 70.degree. C. or higher, and a preferred minimum
temperature of the nematic phase is about -10.degree. C. or lower.
Viscosity of the composition relates to a response time in the
device. A short response time is preferred for displaying moving
images on the device. A shorter response time even by one
millisecond is desirable. Accordingly, small viscosity in the
composition is preferred. Small viscosity at a low temperature is
further preferred. An elastic constant of the composition relates
to a contrast ratio of the device. In order to improve the contrast
ratio of the device, a large elastic constant in the composition is
further preferred.
TABLE-US-00001 TABLE 1 Characteristics of Composition and AM Device
No. Characteristics of Composition Characteristics of AM Device 1
Wide temperature range of a Wide usable temperature range nematic
phase 2 Small viscosity Short response time 3 Suitable optical
anisotropy Large contrast ratio 4 Large positive or negative Low
threshold voltage, small dielectric anisotropy electric power
consumption and large contrast ratio 5 Large specific resistance
Large voltage holding ratio and large contrast ratio 6 High
stability to ultraviolet light Long service life and heat 7 Large
elastic constant Large contrast ratio and short response time
Optical anisotropy of the composition relates to a contrast ratio
in the device. According to a mode of the device, large optical
anisotropy or small optical anisotropy, more specifically, suitable
optical anisotropy is required. A product (.DELTA.n.times.d) of the
optical anisotropy (.DELTA.n) of the composition and a cell gap (d)
in the device is designed so as to maximize the contrast ratio. A
suitable value of the product depends on a type of the operating
mode. In a device having a mode such as TN, a suitable value is
about 0.45 micrometer. In the above case, a composition having the
large optical anisotropy is preferred for a device having a small
cell gap. Large dielectric anisotropy in the composition
contributes to a low threshold voltage, small electric power
consumption and a large contrast ratio in the device. Accordingly,
the large dielectric anisotropy is preferred. Large specific
resistance in the composition contributes to a large voltage
holding ratio and the large contrast ratio in the device.
Accordingly, a composition having the large specific resistance at
room temperature and also at a temperature close to a maximum
temperature of the nematic phase in an initial stage is preferred.
The composition having the large specific resistance at room
temperature and also at a temperature close to the maximum
temperature of the nematic phase after the device has been used for
a long period of time is preferred. Stability of the composition to
ultraviolet light and heat relates to a service life of the device.
In the case where the stability is high, the device has a long
service life. Such characteristics are preferred for an AM device
for use in a liquid crystal projector, a liquid crystal television
and so forth.
Vertical alignment of liquid crystal molecules is achieved by a
specific polyimide alignment film in a general-purpose liquid
crystal display device. In a liquid crystal display device having a
polymer sustained alignment (PSA) mode, the alignment film is
combined with a polymer. First, a composition to which a small
amount of a polymerizable compound is added is injected into the
device. Then, the composition is irradiated with ultraviolet light
while voltage is applied between substrates of the device. The
polymerizable compound is polymerized to form a network structure
of the polymer in the composition. In the composition, alignment of
liquid crystal molecules can be controlled by the polymer, and
therefore the response time of the device is shortened and also
image persistence is improved. Such an effect of the polymer can be
expected for a device having the mode such as the TN mode, the ECB
mode, the OCB mode, the IPS mode, the VA mode, the FFS mode and the
FPA mode.
Meanwhile, in a liquid crystal display device having no alignment
film, a liquid crystal composition containing a polymer and a polar
compound is used. First, a composition to which a small amount of a
polymerizable compound and a small amount of the polar compound are
added is injected into the device. Here, the polar compound is
adsorbed on a substrate surface and is arranged. The liquid crystal
molecules are aligned according to the above arrangement. Then, the
composition is irradiated with ultraviolet light while voltage is
applied between substrates of the device. Here, the polymerizable
compound is polymerized to stabilize the alignment of the liquid
crystal molecules. In the composition, the alignment of the liquid
crystal molecules can be controlled by the polymer and the polar
compound, and therefore the response time of the device is
shortened and image persistence is improved. Further, in a device
having no alignment film, a process of forming the alignment film
is unnecessary. No alignment film is applied thereto, and therefore
no reduction of electric resistance of the device is caused by
interaction between the alignment film and the composition. Such an
effect caused by a combination of the polymer and the polar
compound can be expected for a device having the mode such as the
TN mode, the ECB mode, the OCB mode, the IPS mode, the VA mode, the
FFS mode and the FPA mode.
A composition having positive dielectric anisotropy is used in an
AM device having the TN mode. A composition having negative
dielectric anisotropy is used in an AM device having the VA mode. A
composition having the positive or negative dielectric anisotropy
is used in an AM device having the IPS mode or the FFS mode. A
composition having positive or negative dielectric anisotropy is
used for an AM device having the polymer sustained alignment mode.
In a device having no alignment film, a composition having positive
or negative dielectric anisotropy is used. Examples of the liquid
crystal composition having the positive dielectric anisotropy are
disclosed in Patent literature Nos. 1 to 4 described below, or the
like.
CITATION LIST
Patent Literature
Patent literature No. 1: JP 2013-541028 A
Patent literature No. 2: JP 2013-543526 A
Patent literature No. 3: JP 2014-513150 A
Patent literature No. 4: WO 2014-94959 A
SUMMARY OF INVENTION
Technical Problem
One objective of the invention is a liquid crystal composition that
contains a polymerizable compound (or a polymer thereof) and a
polar compound, and can achieve vertical alignment of liquid
crystal molecules by action of the above compounds. Another
objective is a liquid crystal composition satisfying at least one
of characteristics such as a high maximum temperature of a nematic
phase, a low minimum temperature of the nematic phase, small
viscosity, suitable optical anisotropy, large positive dielectric
anisotropy, large specific resistance, high stability to
ultraviolet light, high stability to heat and a large elastic
constant. Another objective is a liquid crystal composition having
a suitable balance regarding at least two of the characteristics.
Another objective is a liquid crystal display device including such
a composition. Another objective is an AM device having
characteristics such as a short response time, a large voltage
holding ratio, a low threshold voltage, a large contrast ratio and
a long service life.
Solution to Problem
The invention concerns a liquid crystal compound that has positive
dielectric anisotropy, and contains at least one compound selected
from the group of compounds represented by formula (1) as a first
component, a compound represented by formula (2) as a second
component, at least one polar compound as a first additive and at
least one polymerizable compound as a second additive:
##STR00002## wherein, in formula (1), R.sup.1a is alkyl having 1 to
12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12
carbons; ring Q and ring S are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z.sup.1a and
Z.sup.2a are independently a single bond, --CH.sub.2CH.sub.2--,
--CH.dbd.CH--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OCO--,
--CF.sub.2O-- or --OCF.sub.2--; X.sup.1a and X.sup.2a are
independently hydrogen or fluorine; Y.sup.1a is fluorine, chlorine,
alkyl having 1 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine, or
alkenyloxy having 2 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine; q is 1, 2, 3 or 4; s is 0, 1, 2
or 3; and a sum of q and s is 4 or less.
Advantageous Effects of Invention
One advantage of the invention is a liquid crystal composition that
contains a polymerizable compound (or a polymer thereof) and a
polar compound, and can achieve vertical alignment of liquid
crystal molecules by action of the above compounds. Another
advantage is a liquid crystal composition satisfying at least one
of characteristics such as a high maximum temperature of a nematic
phase, a low minimum temperature of the nematic phase, small
viscosity, suitable optical anisotropy, large positive dielectric
anisotropy, large specific resistance, high stability to
ultraviolet light, high stability to heat and a large elastic
constant. Another advantage is a liquid crystal composition having
a suitable balance regarding at least two of the characteristics.
Another advantage is a liquid crystal display device including such
a composition. Another advantage is an AM device having
characteristics such as a short response time, a large voltage
holding ratio, a low threshold voltage, a large contrast ratio and
a long service life.
DESCRIPTION OF EMBODIMENTS
Usage of terms herein is as described below. Terms "liquid crystal
composition" and "liquid crystal display device" may be
occasionally abbreviated as "composition" and "device,"
respectively. "Liquid crystal display device" is a generic term for
a liquid crystal display panel and a liquid crystal display module.
"Liquid crystal compound" is a generic term for a compound having a
liquid crystal phase such as a nematic phase and a smectic phase,
and a compound having no liquid crystal phase but being mixed with
the composition for the purpose of adjusting characteristics such
as a temperature range of the nematic phase, viscosity and
dielectric anisotropy. The compound has a six-membered ring such as
1,4-cyclohexylene and 1,4-phenylene, and has rod-like molecular
structure. "Polymerizable compound" includes a compound to be added
to the composition for the purpose of forming a polymer in the
composition.
The liquid crystal composition is prepared by mixing a plurality of
liquid crystal compounds. An additive is added to the composition
for the purpose of further adjusting characteristics. The additive
such as an optically active compound, an antioxidant, an
ultraviolet light absorber, a dye, an antifoaming agent, the
polymerizable compound, a polymerization initiator, a
polymerization inhibitor and a polar compound is added when
necessary. The liquid crystal compound and the additive are mixed
in such a procedure. A proportion (content) of the liquid crystal
compounds is expressed in terms of weight percent (% by weight)
based on the weight of the liquid crystal composition containing no
additive, even after the additive has been added. A proportion
(amount of addition) of the additive is expressed in terms of
weight percent (% by weight) based on the weight of the liquid
crystal composition containing no additive in a manner similar to
the proportion of the liquid crystal compounds. Weight parts per
million (ppm) may be occasionally used. A proportion of the
polymerization initiator and the polymerization inhibitor is
exceptionally expressed based on the weight of the polymerizable
compound.
"Maximum temperature of the nematic phase" may be occasionally
abbreviated as "maximum temperature." "Minimum temperature of the
nematic phase" may be occasionally abbreviated as "minimum
temperature." An expression "having large specific resistance"
means that the composition has large specific resistance at room
temperature and also at a temperature close to the maximum
temperature in an initial stage, and the composition has the large
specific resistance at room temperature and also at a temperature
close to the maximum temperature even after the device has been
used for a long period of time. An expression "having a large
voltage holding ratio" means that the device has a large voltage
holding ratio at room temperature and also at a temperature close
to the maximum temperature in the initial stage, and the device has
the large voltage holding ratio at room temperature and also at a
temperature close to the maximum temperature even after the device
has been used for the long period of time. In the composition or
the device, the characteristics may be occasionally examined before
and after an aging test (including an acceleration deterioration
test). An expression "increase the dielectric anisotropy" means
that a value of dielectric anisotropy positively increases in a
liquid crystal composition having positive dielectric anisotropy,
and the value of dielectric anisotropy negatively increases in a
liquid crystal composition having negative dielectric
anisotropy.
A compound represented by formula (1) may be occasionally
abbreviated as "compound (1)." At least one compound selected from
the group of compounds represented by formula (1) may be
occasionally abbreviated as "compound (1)." "Compound (1)" means
one compound, a mixture of two compounds or a mixture of three or
more compounds, each represented by formula (1). A same rule
applies also to any other compound represented by any other
formula. An expression "at least one piece of `A`" means that the
number of `A` is arbitrary. An expression "at least one piece of
`A` may be replaced by `B`" means that when the number of `A` is 1,
a position of `A` is arbitrary, and when the number of `A` is 2 or
more, positions thereof can be selected without limitation. A same
rule applies also to an expression "at least one piece of `A` is
replaced by `B`."
A symbol of terminal group R.sup.1a is used for a plurality of
compounds in chemical formulas of component compounds. In the
compounds, two groups represented by any two pieces of R.sup.1a may
be identical or different. In one case, for example, R.sup.1a of
compound (1-1) is ethyl and R.sup.1a of compound (1-2) is ethyl. In
another case, R.sup.1a of compound (1-1) is ethyl and R.sup.1a of
compound (1-2) is propyl. A same rule applies also to a symbol such
as any other terminal groups. In formula (1), when q is 2, two
rings Q exist. In the compound, two rings represented by two rings
Q may be identical or different. A same rule applies also to any
two rings Q when q is larger than 2. A same rule applies also to
any other symbols. A same rule applies also to such a case where
two pieces of Sp.sup.2-P.sup.2 exist in compound (8-27)
Symbols such as A, B, C and D surrounded by a hexagonal shape
correspond to rings such as ring A, ring B, ring C and ring D,
respectively, and represent rings such as a six-membered ring and a
condensed ring. An oblique line crossing the hexagonal shape
represents that arbitrary hydrogen on the ring can be replaced by a
group such as -Sp.sup.1-P.sup.1. A subscript such as `b` represents
the number of groups replaced. When the subscript `b` is 0, no such
replacement exists. When `b` is 2 or more, a plurality of pieces of
-Sp.sup.1-P.sup.1 exist on ring A. The plurality of groups
represented by -Sp.sup.1-P.sup.1 may be identical or different.
Then, 2-fluoro-1,4-phenylene means two divalent groups described
below. In a chemical formula thereof, fluorine may be leftward (L)
or rightward (R). A same rule applies also to an asymmetrical
divalent group formed by removing two hydrogen from a ring, such as
tetrahydropyran-2,5-diyl. A same rule applies also to a divalent
bonding group such as carbonyloxy (--COO or --OCO--).
##STR00003##
An expression "at least one piece of --CH.sub.2-- may be replaced
by --O--" is used herein. In the above case,
--CH.sub.2--CH.sub.2--CH.sub.2-- may be converted into
--O--CH.sub.2--O-- by replacement of non-adjacent --CH.sub.2-- by
--O--. However, a case where adjacent --CH.sub.2-- is replaced by
--O-- is excluded. The reason is that --O--O--CH.sub.2-- (peroxide)
is formed in the replacement. More specifically, the above
expression means both of "one piece of --CH.sub.2-- may be replaced
by --O--" and "at least two pieces of non-adjacent --CH.sub.2-- may
be replaced by --O--." A same rule applies to replacement to --O--,
and also to replacement to a divalent group such as --CH.dbd.CH--
or --COO--. In formula (7), R.sup.4 is alkyl having 4 to 20
carbons, and in the alkyl, at least one piece of --CH.sub.2-- may
be replaced by --CH.dbd.CH-- or the like. The number of carbons of
alkyl is increased by the replacement. In such a case, the maximum
number of carbons is 30. A same rule applies also to alkylene,
cycloalkylene and so forth.
Alkyl of the liquid crystal composition is straight-chain alkyl or
branched-chain alkyl, and includes no cyclic alkyl. Straight-chain
alkyl is preferred to branched-chain alkyl. A same rule applies
also to a terminal group such as alkoxy and alkenyl. With regard to
a configuration of 1,4-cyclohexylene, in general, trans is
preferred to cis. Halogen means fluorine, chlorine, bromine or
iodine. Preferred halogen is fluorine or chlorine. Further
preferred halogen is fluorine.
The invention includes items described below.
Item 1. A liquid crystal compound that has positive dielectric
anisotropy, and contains at least one compound selected from the
group of compounds represented by formula (1) as a first component,
a compound represented by formula (2) as a second component, at
least one polar compound as a first additive and at least one
polymerizable compound as a second additive:
##STR00004## wherein, in formula (1), R.sup.1a is alkyl having 1 to
12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12
carbons; ring Q and ring S are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z.sup.1a and
Z.sup.2a are independently a single bond, --CH.sub.2CH.sub.2--,
--CH.dbd.CH--, --CH.sub.2O--, --OCH.sub.2--, --COO--, --OCO--,
--CF.sub.2O-- or --OCF.sub.2--; X.sup.1a and X.sup.2a are
independently hydrogen or fluorine; Y.sup.1a is fluorine, chlorine,
alkyl having 1 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine, alkoxy having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine, or
alkenyloxy having 2 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine; q is 1, 2, 3 or 4; s is 0, 1, 2
or 3; and a sum of q and s is 4 or less.
Item 2. The liquid crystal composition according to item 1,
containing at least one compound selected from the group of
compounds represented by formula (1-1) to formula (1-14) as the
first component:
##STR00005## wherein, in formula (1-1) to formula (1-14), R.sup.1a
is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or
alkenyl having 2 to 12 carbons; X.sup.1a, X.sup.2a, X.sup.3a,
X.sup.4a, X.sup.5a, X.sup.6a, X.sup.7a, X.sup.8a, X.sup.9a,
X.sup.10a, X.sup.11a, X.sup.12a, X.sup.13a and X.sup.14a are
independently hydrogen or fluorine; and Y.sup.1a is fluorine,
chlorine, alkyl having 1 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine, alkoxy having 1 to 12
carbons in which at least one hydrogen is replaced by fluorine or
chlorine, or alkenyloxy having 2 to 12 carbons in which at least
one hydrogen is replaced by fluorine or chlorine.
Item 3. The liquid crystal composition according to item 1 or 2,
wherein a proportion of the first component is in the range of 5%
by weight to 55% by weight, and a proportion of the second
component is in the range of 5% by weight to 50% by weight, based
on the weight of the liquid crystal composition.
Item 4. The liquid crystal composition according to any one of
items 1 to 3, further containing at least one compound selected
from the group of compounds represented by formula (3) as a third
component:
##STR00006## wherein, in formula (3), R.sup.3a and R.sup.4a are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons, alkenyl having 2 to 12 carbons or alkenyl having 2 to 12
carbons in which at least one hydrogen is replaced by fluorine or
chlorine; ring U and ring V are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene; Z.sup.3a is a single bond,
--CH.sub.2CH.sub.2--, --COO-- or --OCO--; u is 1, 2 or 3; in which,
when u is 1, ring V is 1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene.
Item 5. The liquid crystal composition according to any one of
items 1 to 4, containing at least one compound selected from the
group of compounds represented by formula (3-1) to formula (3-12)
as the third component:
##STR00007## ##STR00008## wherein, in formula (3-1) to formula
(3-12), R.sup.3a and R.sup.4a are independently alkyl having 1 to
12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12
carbons or alkenyl having 2 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine.
Item 6. The liquid crystal composition according to item 4 or 5,
wherein a proportion of the third component is in the range of 3%
by weight to 55% by weight based on the weight of the liquid
crystal composition.
Item 7. The liquid crystal composition according to any one of
items 1 to 6, further containing at least one compound selected
from the group of compounds represented by formula (4) as a fourth
component:
##STR00009## wherein, in formula (4), R.sup.5a is alkyl having 1 to
12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12
carbons; ring W is 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z.sup.4a is a
single bond, --CH.sub.2CH.sub.2--, --COO-- or --OCO--; X.sup.15a
and X.sup.16a are independently hydrogen or fluorine; Y.sup.2a is
fluorine, chlorine, alkyl having 1 to 12 carbons in which at least
one hydrogen is replaced by fluorine or chlorine, alkoxy having 1
to 12 carbons in which at least one hydrogen is replaced by
fluorine or chlorine, or alkenyloxy having 2 to 12 carbons in which
at least one hydrogen is replaced by fluorine or chlorine; and w is
1, 2, 3 or 4.
Item 8. The liquid crystal composition according to any one of
items 1 to 7, containing at least one compound selected from the
group of compounds represented by formula (4-1) to formula (4-16)
as the fourth component:
##STR00010## ##STR00011## wherein, in formula (4-1) to formula
(4-16), R.sup.5a is alkyl having 1 to 12 carbons, alkoxy having 1
to 12 carbons or alkenyl having 2 to 12 carbons.
Item 9. The liquid crystal composition according to item 7 or 8,
wherein a proportion of the fourth component is in the range of 5%
by weight to 50% by weight based on the weight of the liquid
crystal composition.
Item 10. The liquid crystal composition according to any one of
items 1 to 9, containing at least one compound selected from the
group of compounds represented by formula (5) as a fifth
component:
##STR00012## wherein, in formula (5), R.sup.6a and R.sup.7a are
independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons, alkenyl having 2 to 12 carbons or alkenyloxy having 2 to
12 carbons; ring D and ring F are independently 1,4-cyclohexylene,
1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least
one hydrogen is replaced by fluorine or chlorine, or
tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene,
2-chloro-3-fluoro-1,4-phenylene,
2,3-difluoro-5-methyl-1,4-phenylene,
3,4,5-trifluoronaphthalene-2,6-diyl or
7,8-difluorochroman-2,6-diyl; Z.sup.5a and Z.sup.6a are
independently a single bond, --CH.sub.2CH.sub.2--, --COO--,
--OCO--, --CH.sub.2O-- or --OCH.sub.2--; e is 1, 2 or 3, and f is 0
or 1; and a sum of e and f is 3 or less.
Item 11. The liquid crystal composition according to any one of
items 1 to 10, containing at least one compound selected from the
group of compounds represented by formula (5-1) to formula (5-21)
as the fifth component:
##STR00013## ##STR00014## ##STR00015## wherein, in formula (5-1) to
formula (5-21), R.sup.6a and R.sup.7a are independently alkyl
having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl
having 2 to 12 carbons or alkenyloxy having 2 to 12 carbons.
Item 12. The liquid crystal composition according to item 10 or 11,
wherein a proportion of the fifth component is in the range of 3%
by weight to 25% by weight based on the weight of the liquid
crystal composition.
Item 13. The liquid crystal composition according to any one of
items 1 to 12, wherein the first additive is a polar compound
having a polar group containing a hetero atom selected from
nitrogen, oxygen, sulfur and phosphorus.
Item 14. The liquid crystal composition according to any one of
items 1 to 13, containing at least one polar compound selected from
the group of compounds represented by formula (6) and formula (7)
as the first additive: MES-R.sup.5 (6) (R.sup.4).sub.g--R.sup.5 (7)
wherein, in formula (6), MES is a mesogen group having at least one
ring; in formula (7), R.sup.4 is alkyl having 4 to 20 carbons, and
in the alkyl, at least one piece of --CH.sub.2-- may be replaced by
--CH.dbd.CH--, --CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or
cycloalkylene having 3 to 8 carbons, and in the groups, at least
one hydrogen may be replaced by fluorine or chlorine; and in
formula (6) and formula (7), R.sup.5 is a polar group having at
least one of an oxygen atom having an OH structure, a sulfur atom
having an SH structure, and a nitrogen atom having a primary,
secondary or tertiary amine structure; and g is 1 or 2.
Item 15. The liquid crystal composition according to any one of
items 1 to 14, containing at least one compound selected from the
group of compounds represented by formula (6-1) as the first
additive:
##STR00016## wherein, in formula (6-1), ring G and ring I are
independently an aromatic group having 6 to 25 carbons, a
heteroaromatic group having 5 to 25 carbons, an alicyclic group
having 3 to 25 carbons or a heteroalicyclic group having 4 to 25
carbons, and the groups may be a condensed ring, and in the groups,
at least one hydrogen may be replaced by group T, in which group T
is --OH, --(CH.sub.2).sub.i--OH, halogen, --CN, --NO.sub.2, --NCO,
--NCS, --OCN, --SCN, --C(.dbd.O)N(R.sup.0).sub.2,
--C(.dbd.O)R.sup.0, --N(R.sup.0).sub.2,
--(CH.sub.2).sub.i--N(R.sup.0).sub.2, aryl having 6 to 20 carbons,
heteroaryl having 6 to 20 carbons, alkyl having 1 to 25 carbons,
alkoxy having 1 to 25 carbons, alkylcarbonyl having 2 to 25
carbons, alkoxycarbonyl having 2 to 25 carbons, alkylcarbonyloxy
having 2 to 25 carbons or alkoxycarbonyloxy having 2 to 25 carbons,
and in the groups, at least one hydrogen may be replaced by
fluorine or chlorine, in which R.sup.0 is hydrogen or alkyl having
1 to 12 carbons, and i is 1, 2, 3 or 4; Z.sup.5 is --O--, --S--,
--CO--, --CO--O--, --OCO--, --O--CO--O--, --OCH.sub.2--,
--CH.sub.2O--, --SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--,
--OCF.sub.2--, --CF.sub.2S--, --SCF.sub.2--, --(CH.sub.2).sub.i--,
--CF.sub.2CH.sub.2--, --CH.sub.2CF.sub.2--, --(CF.sub.2).sub.i--,
--CH.dbd.CH--, --CF.dbd.CF, --C.ident.C--, --CH.dbd.CH--COO--,
--OCO--CH.dbd.CH--, --C(R.sup.0).sub.2 or a single bond, in which
R.sup.0 is hydrogen or alkyl having 1 to 12 carbons, and i is 1, 2,
3 or 4; R.sup.5 is alkyl having 1 to 25 carbons, and in the alkyl,
at least one piece of --CH.sub.2-- may be replaced by --NR.sup.0--,
--O--, --S--, --CO--, --COO--, --OCO--, --OCOO-- or cycloalkylene
having 3 to 8 carbons, in which R.sup.0 is hydrogen or alkyl having
1 to 12 carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.5 has at least one
of an oxygen atom having an OH structure, a sulfur atom having an
SH structure, and a nitrogen atom having a primary, secondary or
tertiary amine structure; R.sup.6 is hydrogen, halogen and alkyl
having 1 to 25 carbons, and in the alkyl, at least one piece of
--CH.sub.2-- may be replaced by --NR.sup.0--, --O--, --S--, --CO--,
--CO--O--, --O--CO--, --O--CO--O-- or cycloalkylene having 3 to 8
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and in the groups, at least
hydrogen may be replaced by fluorine or chlorine, in which R.sup.0
is hydrogen or alkyl having 1 to 12 carbons; and h is 0, 1, 2, 3, 4
or 5.
Item 16. The liquid crystal composition according to any one of
items 1 to 15, further containing at least one polar compound
selected from the group of compounds represented by formula (7-1)
as the first additive: R.sup.4-R.sup.5 (7-1) wherein, in formula
(7-1), R.sup.4 is alkyl having 4 to 20 carbons, and in the alkyl,
at least one piece of --CH.sub.2-- may be replaced by
--CH.dbd.CH--, --CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or
cycloalkylene having 3 to 8 carbons, and in the groups, at least
one hydrogen may be replaced by fluorine or chlorine; R.sup.5 is
alkyl having 1 to 25 carbons, and in the alkyl, at least one piece
of --CH.sub.2-- may be replaced by --NR.sup.0--, --O--, --S--,
--CO--, --COO--, --OCO--, --OCOO-- or cycloalkylene having 3 to 8
carbons, in which R.sup.0 is hydrogen or alkyl having 1 to 12
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.5 has at least one
of an oxygen atom having an OH structure, a sulfur atom having an
SH structure, and a nitrogen atom having a primary, secondary or
tertiary amine structure.
Item 17. The liquid crystal composition according to any one of
items 14 to 16, wherein, in formula (6) and formula (7) according
to item 14, R.sup.5 is a group represented by any one of formula
(A1) to formula (A4):
##STR00017## wherein, in formula (A1) to formula (A4), Sp.sup.4,
Sp.sup.6 and Sp.sup.7 are independently a single bond or a group
(-Sp''-X''--), in which Sp'' is alkylene having 1 to 20 carbons,
and in the alkylene, at least one piece of --CH.sub.2-- may be
replaced by --O--, --S--, --NH--, --N(R.sup.0)--, --CO--,
--CO--O--, --O--CO--, --O--CO--O--, --S--CO--, --CO--S--,
--N(R.sup.0)--CO--O--, --O--CO--N(R.sup.0)--,
--N(R.sup.0)--CO--N(R.sup.0)--, --CH.dbd.CH-- or --C.ident.C--, and
in the groups, at least one hydrogen may be replaced by fluorine,
chlorine or --CN, and X'' is --O--, --S--, --CO--, --CO--O--,
--O--CO--, --O--CO--O--, --CO--N(R.sup.0)--, --N(R.sup.0)--CO--,
--N(R.sup.0)--CO--N(R.sup.0)--, --OCH.sub.2--, --CH.sub.2O--,
--SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--,
--CF.sub.2S--, --SCF.sub.2--, --CF.sub.2CH.sub.2--,
--CH.sub.2CF.sub.2--, --CF.sub.2CF.sub.2--, --CH.dbd.N--,
--N.dbd.CH--, --N.dbd.N--, --CH.dbd.CR.sup.0--,
--CY.sup.2.dbd.CY.sup.3--, --C.ident.C--, --CH.dbd.CH--CO--O--,
--O--CO--CH.dbd.CH-- or a single bond, in which R.sup.0 is hydrogen
or alkyl having 1 to 12 carbons, and Y.sup.2 and Y.sup.3 are
independently hydrogen, fluorine, chlorine or --CN; Sp.sup.5 is
>CH--, >CR.sup.11--, >N-- or >C<; X.sup.3 is --OH,
--OR.sup.11, --COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2,
--SH, --SR,
##STR00018## in which R.sup.0 is hydrogen or alkyl having 1 to 12
carbons; X.sup.4 is --O--, --CO--, --NH--, --NR.sup.11--, --S-- or
a single bond; Z.sup.6 is alkylene having 1 to 15 carbons, an
alicyclic group having 5 or 6 carbons or a combination thereof, and
in the groups, at least one hydrogen may be replaced by --OH,
--OR.sup.11, --COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2,
fluorine or chlorine, in which R.sup.11 is alkyl having 1 to 15
carbons, and in the alkyl, at least one piece of --CH.sub.2-- may
be replaced by --C.ident.C--, --CH.dbd.CH--, --COO--, --OCO--,
--CO-- or --O--, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine; ring J is an aromatic group
having 6 to 25 carbons or an alicyclic group having 3 to 25
carbons, and the groups may be a condensed ring, and in the groups,
one to three hydrogens may be replaced by R.sup.L; R.sup.L is --OH,
--(CH.sub.2).sub.i--OH, fluorine, chlorine, --CN, --NO.sub.2,
--NCO, --NCS, --OCN, --SCN, --C(.dbd.O)N(R.sup.0).sub.2,
--C(.dbd.O)R.sup.0, --N(R.sup.0).sub.2,
--(CH.sub.2).sub.i--N(R.sup.0).sub.2, --SH, --SR.sup.0, aryl having
6 to 20 carbons, heteroaryl having 6 to 20 carbons, alkyl having 1
to 25 carbons, alkoxy having 1 to 25 carbons, alkylcarbonyl having
2 to 25 carbons, alkoxycarbonyl having 2 to 25 carbons,
alkylcarbonyloxy having 2 to 25 carbons or alkoxycarbonyloxy having
2 to 25 carbons, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.0 is hydrogen or
alkyl having 1 to 12 carbons, and i is 1, 2, 3 or 4; j is 0, 1, 2
or 3; and k is 2, 3, 4 or 5.
Item 18. The liquid crystal composition according to item 15 or 17,
wherein the first additive is at least one compound selected from
the group of compounds represented by formula (6-1-1) to formula
(6-1-4):
##STR00019## wherein, in formula (6-1-1) to formula (6-1-4), ring G
and ring I are independently 1,4-cyclohexylene, 1,4-phenylene,
2-fluoro-1,4-phenylene, 2-fluoro-1,3-phenylene,
2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene,
2-trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene or
2,3,5,6-tetrafluoro-1,4-phenylene; ring J is cyclohexyl or phenyl;
Z.sup.6 is a single bond, --CH.sub.2CH.sub.2--, --COO-- or --OCO--;
Z.sup.7 is a single bond, alkylene having 1 to 15 carbons, an
alicyclic group having 5 or 6 carbons or a combination thereof, and
in the groups, at least one hydrogen may be replaced by --OH,
--OR.sup.11, --COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2,
fluorine or chlorine, and R.sup.11 is alkyl having 1 to 15 carbons,
and in the alkyl, at least one piece of --CH.sub.2-- may be
replaced by --C.ident.C--, --CH.dbd.CH--, --COO--, --OCO--, --CO--,
--O-- or --NH--, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine; Sp.sup.4 is a single bond,
--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2--, --CH.sub.2O--
or --OCH.sub.2--; Sp.sup.7 is a single bond or alkylene having 1 to
5 carbons, and in the alkylene, --CH.sub.2-- may be replaced by
--O-- or --NH--; R.sup.7 is alkyl having 1 to 8 carbons or
fluorine; h is 0, 1, 2, 3, 4 or 5; X.sup.3 is --OH, --COOH, --SH,
--OCH.sub.3 or --NH.sub.2; and X.sup.4 is a single bond or
--O--.
Item 19. The liquid crystal composition according to item 16 or 17,
wherein the first additive is at least one compound selected from
the group of compounds represented by formula (7-1-1) to formula
(7-1-29):
##STR00020## ##STR00021## wherein, in formula (7-1-1) to formula
(7-1-29), R.sup.4 is alkyl having 4 to 20 carbons, and in the
alkyl, at least one piece of --CH.sub.2-- may be replaced by
--CH.dbd.CH--, --CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or
cycloalkylene having 3 to 8 carbons, and in the groups, at least
one hydrogen may be replaced by fluorine or chlorine.
Item 20. The liquid crystal composition according to any one of
items 1 to 19, wherein a proportion of the first additive is 10% by
weight or less based on the weight of the liquid crystal
composition.
Item 21. The liquid crystal composition according to any one of
items 1 to 20, containing at least one polymerizable compound
selected from the group of compounds represented by formula (8) as
the second additive:
##STR00022## wherein, in formula (8), ring A and ring C are
independently cyclohexyl, cyclohexenyl, phenyl, l-naphthyl,
2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl
or pyridine-2-yl, and in the rings, at least one hydrogen may be
replaced by fluorine, chlorine, alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine;
ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene,
naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl,
naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl,
naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl,
naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl,
1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and
in the rings, at least one hydrogen may be replaced by fluorine,
chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12
carbons, or alkyl having 1 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine; Z.sup.1 and Z.sup.2
are independently a single bond or alkylene having 1 to 10 carbons,
and in the alkylene, at least one piece of --CH.sub.2-- may be
replaced by --O--, --CO--, --COO-- or --OCO--, and at least one
piece of --CH.sub.2CH.sub.2-- may be replaced by --CH.dbd.CH--,
--C(CH.sub.3).dbd.CH--, --CH.dbd.C(CH.sub.3)-- or
--C(CH.sub.3).dbd.C(CH.sub.3)--, and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine; P.sup.1, P.sup.2
and P.sup.3 are a polymerizable group; Sp.sup.1, Sp.sup.2 and
Sp.sup.3 are independently a single bond or alkylene 1 to 10
carbons, and in the alkylene, at least one piece of --CH.sub.2--
may be replaced by --O--, --COO--, --OCO-- or --OCOO--, and at
least one piece of --CH.sub.2CH.sub.2-- may be replaced by
--CH.dbd.CH-- or --C.ident.C--, and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine; a is 0, 1 or 2;
and b, c and d are independently 0, 1, 2, 3 or 4.
Item 22. The liquid crystal composition according to item 21,
wherein, in formula (8) according to item 21, P.sup.1, P.sup.2 and
P.sup.3 are independently a polymerizable group selected from the
group of groups represented by formula (P-1) to formula (P-5):
##STR00023## wherein, in formula (P-1) to formula (P-5), M.sup.1,
M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl
having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at
least one hydrogen is replaced by fluorine or chlorine.
Item 23. The liquid crystal composition according to any one of
items 1 to 22, wherein the second additive is at least one
polymerizable compound selected from the group of compounds
represented by formula (8-1) to formula (8-28):
##STR00024## ##STR00025## ##STR00026## wherein, in formula (8-1) to
formula (8-28), P.sup.1, P.sup.2 and P.sup.3 are independently a
polymerizable group selected from the group of groups represented
by formula (P-1) to formula (P-3), in which M.sup.1, M.sup.2 and
M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5
carbons, or alkyl having 1 to 5 carbons in which at least one
hydrogen is replaced by fluorine or chlorine;
##STR00027## wherein, Sp.sup.1, Sp.sup.2 and Sp.sup.3 are
independently a single bond or alkylene having 1 to 10 carbons, and
in the alkylene, at least one piece of --CH.sub.2-- may be replaced
by --O--, --COO--, --OCO-- or --OCOO--, and at least one piece of
--CH.sub.2CH.sub.2-- may be replaced by --CH.dbd.CH-- or
--C.ident.C--, and in the groups, at least one hydrogen may be
replaced by fluorine or chlorine.
Item 24. The liquid crystal composition according to any one of
items 21 to 23, wherein a proportion of the second additive is in
the range of 0.03% by weight to 10% by weight based on the weight
of the liquid crystal composition.
Item 25. A liquid crystal display device, including the liquid
crystal composition according to any one of items 1 to 24.
Item 26. The liquid crystal display device according to item 25,
wherein an operating mode in the liquid crystal display device
includes an IPS mode, a TN mode, an FFS mode or an FPA mode, and a
driving mode in the liquid crystal display device includes an
active matrix mode.
Item 27. A polymer sustained alignment mode liquid crystal display
device, wherein the liquid crystal display device includes the
liquid crystal composition according to any one of items 1 to 24,
or a polymerizable compound in the liquid crystal composition is
polymerized.
Item 28. A polymer sustained alignment mode liquid crystal display
device having no alignment film, wherein the liquid crystal display
device includes the liquid crystal composition according to any one
of items 1 to 24, or a polymerizable compound in the liquid crystal
composition is polymerized.
Item 29. Use of the liquid crystal composition according to any one
of items 1 to 24 in a liquid crystal display device.
Item 30. Use of the liquid crystal composition according to any one
of items 1 to 24 in a polymer sustained alignment mode liquid
crystal display device.
Item 31. Use of the liquid crystal composition according to any one
of items 1 to 24 in a liquid crystal display device having no
alignment film.
The invention further includes the following items: (a) a method of
producing the liquid crystal display device by arranging the liquid
crystal composition between two substrates, irradiating the
composition with light while applying voltage to the composition,
and polymerizing a polymerizable compound contained in the
composition; and (b) the liquid crystal composition, wherein a
maximum temperature of a nematic phase is 70.degree. C. or higher,
optical anisotropy (measured at 25.degree. C.) at a wavelength of
589 nanometers is 0.08 or more and dielectric anisotropy (measured
at 25.degree. C.) at a frequency of 1 kHz is 2 or more.
The invention further includes the following items: (c) the
composition containing at least two polymerizable compounds (8)
described above; (d) the composition further containing a
polymerizable compound different from polymerizable compounds (8)
described above; (e) the composition, further containing one, two
or at least three additives, such as an optically active compound,
an antioxidant, an ultraviolet light absorber, a dye, an
antifoaming agent, a polymerizable compound, a polymerization
initiator, a polymerization inhibitor and a polar compound; (f) an
AM device including the composition; (g) a device including the
composition, and having a TN, ECB, OCB, IPS, FFS, VA or FPA mode;
(h) a transmissive device including the composition; (i) use of the
composition as the composition having the nematic phase; and (j)
use as an optically active composition by adding the optically
active compound to the composition.
The composition of the invention will be described in the following
order. First, a constitution of the composition will be described.
Second, main characteristics of the component compounds and main
effects of the compounds on the composition will be described.
Third, a combination of components in the composition, a preferred
proportion of the components and the basis thereof will be
described. Fourth, a preferred embodiment of the component
compounds will be described. Fifth, a preferred component compounds
will be described. Sixth, an additive that may be added to the
composition will be described. Seventh, methods for synthesizing
the component compounds will be described. Last, an application of
the composition will be described.
First, the constitution of the composition will be described. The
composition of the invention is classified into composition A and
composition B. Composition A may further contain any other liquid
crystal compound, an additive or the like in addition to the liquid
crystal compound selected from compound (1), compound (2), compound
(3), compound (4) and compound (5). "Any other liquid crystal
compound" means a liquid crystal compound different from compound
(1) to compound (5). Such a compound is mixed with the composition
for the purpose of further adjusting the characteristics. The
additive is the optically active compound, the antioxidant, the
ultraviolet light absorber, the dye, the antifoaming agent, the
polymerizable compound, the polymerization initiator, the
polymerization inhibitor, the polar compound or the like.
Composition B consists essentially of the liquid crystal compound
selected from compound (1) to compound (5). An expression
"essentially" means that the composition may contain the additive,
but contains no any other liquid crystal compound. Composition B
has a smaller number of components than composition A has.
Composition B is preferred to composition A in view of cost
reduction. Composition A is preferred to composition B in view of
possibility of further adjusting the characteristics by mixing any
other liquid crystal compound. An example of composition B is a
mixture of compound (1) and compound (2). The mixture may further
contain one or two compounds selected from compound (3), compound
(4) and compound (5).
Second, the main characteristics of the component compounds and the
main effects of the compounds on the characteristics of the
composition will be described. The main characteristics of the
component compounds are summarized in Table 2 on the basis of
advantageous effects of the invention. In Table 2, a symbol L
stands for "large" or "high," a symbol M stands for "medium" and a
symbol S stands for "small" or "low." The symbols L, M and S
represent a classification based on a qualitative comparison among
the component compounds, and symbol 0 (zero) means that a value is
zero or close to zero.
TABLE-US-00002 TABLE 2 Characteristics of Compounds Characteristics
(1) (2) (3) (4) (5) Maximum temperature S to L M S to L S to L S to
M Viscosity M to L S S to M M to L L Optical anisotropy M to L S M
to L M to L M to L Dielectric anisotropy L.sup.1) 0 0 S to L.sup.1)
L.sup.2) Specific resistance L L L L L .sup.1)A value of dielectric
anisotropy is positive, and the symbol represents magnitude of an
absolute value. .sup.2)A value of dielectric anisotropy is
negative, and the symbol represents magnitude of an absolute
value.
Upon mixing the component compounds with the composition, the main
effects of the component compounds on the characteristics of the
composition are as described below. Compound (1) increases the
dielectric anisotropy. Compound (2) decreases the viscosity.
Compound (3) increases the maximum temperature or decreases the
minimum temperature. Compound (4) increases the dielectric
anisotropy and decreases the minimum temperature. Compound (5)
increases the dielectric constant in a minor axis direction.
Compound (6) and compound (7) are adsorbed on a substrate surface
by action of the polar group, and control alignment of liquid
crystal molecules. Compound (8) gives a polymer by polymerization.
The polymer stabilizes the alignment of the liquid crystal
molecules, and therefore shortens a response time of the device and
improves image persistence. A polymer of compound (8) is effective
in view of the alignment of the liquid crystal molecules. Compound
(6) or compound (7) is also effective. A combination of compound
(8) and compound (6) or a combination of compound (8) and compound
(7) is further effective. A synergistic effect can be expected by
the combination. A better long-term stability than the stability of
compound (6) only or compound (7) only can be expected by the
combination.
Third, the combination of components in the composition, the
preferred proportion of the components and the basis thereof will
be described. Preferred combinations of components in the
composition include a combination of compound (1), compound (2),
compound (3), compound (6) and compound (8), a combination of
compound (1), compound (2), compound (3), compound (7) and compound
(8), a combination of compound (1), compound (2), compound (4),
compound (6) and compound (8), a combination of compound (1),
compound (2), compound (4), compound (7) and compound (8), a
combination of compound (1), compound (2), compound (3), compound
(6), compound (7) and compound (8) or a combination of compound
(1), compound (2), compound (4), compound (6), compound (7) and
compound (8).
Another preferred combinations of components include a combination
of compound (1), compound (2), compound (3), compound (4), compound
(6) and compound (8), a combination of compound (1), compound (2),
compound (3), compound (4), compound (7) and compound (8), a
combination of compound (1), compound (2), compound (3), compound
(4), compound (6), compound (7) and compound (8), a combination of
compound (1), compound (2), compound (3), compound (5), compound
(6) and compound (8), a combination of compound (1), compound (2),
compound (3), compound (5), compound (7) and compound (8) or a
combination of compound (1), compound (2), compound (3), compound
(5), compound (6), compound (7) and compound (8).
Another preferred combination of components includes a combination
of compound (1), compound (2), compound (4), compound (5), compound
(6) and compound (8), a combination of compound (1), compound (2),
compound (4), compound (5), compound (7) and compound (8), a
combination of compound (1), compound (2), compound (4), compound
(5), compound (6), compound (7) and compound (8), a combination of
compound (1), compound (2), compound (3), compound (4), compound
(5), compound (6) and compound (8), a combination of compound (1),
compound (2), compound (3), compound (4), compound (5), compound
(7) and compound (8) or a combination of compound (1), compound
(2), compound (3), compound (4), compound (5), compound (6),
compound (7) and compound (8). A further preferred combination
includes a combination of compound (1), compound (2), compound (3),
compound (4), compound (6) and compound (8).
A preferred proportion of compound (1) is about 5% by weight or
more for increasing the dielectric anisotropy, and about 55% by
weight or less for decreasing the minimum temperature or for
decreasing the viscosity. A further preferred proportion is in the
range of about 5% by weight to about 45% by weight. A particularly
preferred proportion is in the range of about 10% by weight to
about 35% by weight.
A preferred proportion of compound (2) is about 5% by weight or
more for decreasing the viscosity, and about 50% by weight or less
for increasing the dielectric anisotropy. A further preferred
proportion is in the range of about 5% by weight to about 40% by
weight. A particularly preferred proportion is in the range of
about 10% by weight to about 30% by weight.
A preferred proportion of compound (3) is about 3% by weight or
more for increasing the maximum temperature or for decreasing the
viscosity, and about 55% by weight or less for increasing the
dielectric anisotropy. A further preferred proportion is in the
range of about 5% by weight to about 45% by weight. A particularly
preferred proportion is in the range of about 5% by weight to about
35% by weight.
A preferred proportion of compound (4) is about 5% by weight for
increasing the dielectric anisotropy, and about 50% by weight or
less for decreasing the minimum temperature. A further preferred
proportion is in the range of about 5% by weight to about 40% by
weight. A particularly preferred proportion is in the range of
about 5% by weight to about 25% by weight.
A preferred proportion of compound (5) is about 3% by weight or
more for increasing the dielectric anisotropy, and about 25% by
weight or less for decreasing the minimum temperature. A further
preferred proportion is in the range of about 5% by weight to about
20% by weight. A particularly preferred proportion is in the range
of about 5% by weight to about 15% by weight.
Compound (6) or compound (7) is added to the composition for the
purpose of controlling the alignment of the liquid crystal
molecules. A preferred proportion of compound (6) or compound (7)
is about 0.05% by weight or more for aligning the liquid crystal
molecules, and about 10% by weight or less for preventing poor
display of the device. A further preferred proportion is in the
range of about 0.1% by weight to about 7% by weight. A particularly
preferred proportion is in the range of about 0.5% by weight to
about 5% by weight.
Compound (8) is added to the composition for the purpose of
adapting the composition to the polymer sustained alignment mode
device. A preferred proportion of compound (8) is about 0.03% by
weight or more for improving long-term reliability of the device,
and about 10% by weight or less for preventing the poor display of
the device. A further preferred proportion is in the range of about
0.1% by weight to about 2% by weight. A particularly preferred
proportion is in the range of about 0.2% by weight to about 1.0% by
weight.
Fourth, the preferred embodiment of the component compounds will be
described. In formula (1), formula (3), formula (4) and formula
(5), R.sup.1a and R.sup.5a are independently alkyl having 1 to 12
carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12
carbons. Preferred R.sup.1a or R.sup.5a is alkyl having 1 to 12
carbons for increasing stability to ultraviolet light or heat.
R.sup.3a and R.sup.4a are independently alkyl having 1 to 12
carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12
carbons, or alkenyl having 2 to 12 carbons in which at least one
hydrogen is replaced by fluorine or chlorine. Preferred R.sup.3a or
R.sup.4a is alkyl having 1 to 12 carbons for increasing the
stability to ultraviolet light or heat, and alkenyl having 2 to 12
carbons for decreasing the minimum temperature or for decreasing
the viscosity.
R.sup.6a and R.sup.7a are independently alkyl having 1 to 12
carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12
carbons or alkenyloxy having 2 to 12 carbons. Preferred R.sup.6a or
R.sup.7a is alkyl having 1 to 12 carbons for increasing the
stability, and alkoxy having 1 to 12 carbons for increasing the
dielectric anisotropy. Alkyl is straight-chain alkyl or
branched-chain alkyl, but includes no cyclic alkyl. Straight-chain
alkyl is preferred to branched-chain alkyl. A same rule applies
also to a terminal group such as alkoxy and alkenyl.
Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl or octyl. Further preferred alkyl is ethyl, propyl, butyl,
pentyl or heptyl for decreasing the viscosity.
Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy,
hexyloxy or heptyloxy. Further preferred alkoxy is methoxy or
ethoxy for decreasing the viscosity.
Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl,
2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or
5-hexenyl. Further preferred alkenyl is vinyl, 1-propenyl,
3-butenyl or 3-pentenyl for decreasing the viscosity. A preferred
configuration of --CH.dbd.CH-- in the alkenyl depends on a position
of a double bond. For decreasing the viscosity, and so forth, in
alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl,
3-pentenyl and 3-hexenyl, trans is preferred. Cis is preferred in
alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.
Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy,
3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy is
allyloxy or 3-butenyloxy for decreasing the viscosity.
Preferred examples of alkenyl in which at least one hydrogen is
replaced by fluorine or chlorine include 2,2-difluorovinyl,
3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl,
5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. Further
preferred examples include 2,2-difluorovinyl or
4,4-difluoro-3-butenyl for decreasing the viscosity.
Ring Q and ring S are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Preferred ring Q
or ring S is 1,4-phenylene, 2-fluoro-1,4-phenylene or
2,6-difluoro-1,4-phenylene for increasing the optical anisotropy.
Ring U and ring V are independently 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene, in which, when u is 1, ring V is
1,4-phenylene, 2-fluoro-1,4-phenylene or
2,5-difluoro-1,4-phenylene. Preferred ring U or ring V is
1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene
for increasing the optical anisotropy. Ring W is 1,4-cyclohexylene,
1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene,
2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl,
1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Preferred ring W
is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the
optical anisotropy.
Ring D and ring F are independently 1,4-cyclohexylene,
1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least
one hydrogen is replaced by fluorine or chlorine, or
tetrahydropyran-2,5-diyl. Preferred ring D or ring F is
1,4-cyclohexylene for decreasing the viscosity,
tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy,
and 1,4-phenylene for increasing the optical anisotropy. Ring E is
2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene,
2,3-difluor-5-methyl-1,4-phenylene,
3,4,5-trifluoronaphthalene-2,6-diyl or
7,8-difluorochroman-2,6-diyl. Preferred ring E is
2,3-difluoro-1,4-phenylene for increasing the dielectric
anisotropy. With regard to the configuration of 1,4-cyclohexylene,
trans is preferred to cis for increasing the maximum temperature.
Tetrahydropyran-2,5-diyl includes:
##STR00028## preferably
##STR00029##
Then, q is 1, 2, 3 or 4, and s is 0, 1, 2 or 3, and a sum of q and
s is 4 or less. Preferred q is 2 or 3 for increasing the dielectric
anisotropy. Preferred s is 0 or 1 for decreasing the minimum
temperature. Then, u is 1, 2 or 3. Preferred u is 1 for decreasing
the viscosity, and 2 for decreasing the minimum temperature. Then,
w is 1, 2, 3 or 4. Preferred w is 2 or 3 for increasing the
dielectric anisotropy. Then, e is 1, 2 or 3, f is 0 or 1, and a sum
of e and f is 3 or less. Preferred e is 1 for decreasing the
viscosity, and 2 or 3 for increasing the maximum temperature.
Preferred f is 0 for decreasing the viscosity, and 1 for decreasing
the minimum temperature.
Z.sup.1a and Z.sup.2a are independently a single bond,
--CH.sub.2CH.sub.2--, --CH.dbd.CH--, --CH.sub.2O--, --OCH.sub.2--,
--COO--, --OCO--, --CF.sub.2O-- or --OCF.sub.2--. Preferred
Z.sup.1a or Z.sup.2a is a single bond for decreasing the viscosity.
Z.sup.3a is a single bond, --CH.sub.2CH.sub.2--, --COO-- or
--OCO--. Preferred Z.sup.3a is a single bond for decreasing the
viscosity. Z.sup.4a is a single bond, --CH.sub.2CH.sub.2--, --COO--
or --OCO--. Preferred Z.sup.4a is a single bond for decreasing the
viscosity. Z.sup.5a and Z.sup.6a are independently a single bond,
--CH.sub.2CH.sub.2--, --COO--, --OCO--, --CH.sub.2O-- or
--OCH.sub.2--. Preferred Z.sup.5a or Z.sup.6a is a single bond for
decreasing the viscosity, and --CH.sub.2O-- or --OCH.sub.2-- for
increasing the dielectric anisotropy.
X.sup.1a, X.sup.2a, X.sup.3a, X.sup.4a, X.sup.5a, X.sup.6a,
X.sup.7a, X.sup.8a, X.sup.9a, X.sup.10a, X.sup.11a, X.sup.12a,
X.sup.13a, X.sup.14a, X.sup.15a and X.sup.16a are independently
hydrogen or fluorine. Preferred X.sup.1a, X.sup.2a, X.sup.3a,
X.sup.4a, X.sup.5a, X.sup.6a, X.sup.7a, X.sup.8a, X.sup.9a,
X.sup.10a, X.sup.11a, X.sup.12a, X.sup.13a, X.sup.14a, X.sup.15a or
X.sup.16a is fluorine for increasing the dielectric anisotropy.
Y.sup.1a and Y.sup.2a are independently fluorine, chlorine, alkyl
having 1 to 12 carbons in which at least one hydrogen is replaced
by fluorine or chlorine, alkoxy having 1 to 12 carbons in which at
least one hydrogen is replaced by fluorine or chlorine, or
alkenyloxy having 2 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine. Preferred Y.sup.1a or Y.sup.2a is
fluorine for decreasing the minimum temperature. Preferred examples
of the alkyl in which at least one hydrogen is replaced by fluorine
or chlorine include trifluoromethyl. Preferred examples of the
alkoxy in which at least one hydrogen is replaced by fluorine or
chlorine include trifluoromethoxy. Preferred examples of the
alkenyloxy in which at least one hydrogen is replaced by fluorine
or chlorine include trifluorovinyloxy.
In formula (6) and formula (7), R.sup.5 is a polar group. The polar
compound is added to the composition, and therefore is preferably
stable. When the polar compound is added to the composition, the
compound preferably does not decrease the voltage holding ratio of
the device. The polar compound preferably has low volatility.
Preferred molar mass is 130 g/mol or more. Further preferred molar
mass is in the range of 150 g/mol to 500 g/mol. A preferred polar
compound has no polymerizable group such as acryloyloxy
(--OCO--CH.dbd.CH.sub.2) and methacryloyloxy
(--OCO--(CH.sub.3)C--CH.sub.2).
The polar group has noncovalent bond interaction with a surface of
a glass substrate or a metal oxide film. A preferred polar group
includes a hetero atom selected from nitrogen, oxygen, sulfur and
phosphorus. A preferred polar group includes at least one or at
least two hetero atoms. A further preferred polar group is a
monovalent group derived therefrom by eliminating hydrogen from a
compound selected from the group of alcohol, primary, secondary and
tertiary amine, ketone, carboxylic acid, thiol, ester, ether,
thioether and a combination thereof. The groups may have a
straight-chain structure, a branched-chain structure, a cyclic
structure or a combination thereof. A particularly preferred polar
group has at least one oxygen atom having an OH structure or at
least one nitrogen atom having a primary, secondary or tertiary
amine structure.
Examples of polar group R.sup.5 include a group represented by
formula (A1) to formula (A4).
##STR00030##
In formula (A1) to formula (A4), Sp.sup.4, Sp.sup.6 and Sp.sup.7
are independently a single bond or a group (-Sp''-X''--), and X''
is bonded to an MES group or R.sup.4. Sp'' is alkylene having 1 to
20 carbons, and is preferably alkylene having 1 to 12 carbons, and
in the alkylene, at least one piece of --CH.sub.2-- may be replaced
by --O--, --S--, --NH--, --N(R.sup.0)--, --CO--, --CO--O--,
--O--CO--, --O--CO--O--, --S--CO--, --CO--S--,
--N(R.sup.0)--CO--O--, --O--CO--N(R.sup.0)--,
--N(R.sup.0)--CO--N(R.sup.0)--, --CH.dbd.CH-- or --C.ident.C--, and
in the groups, at least one hydrogen may be replaced by fluorine,
chlorine or --CN, and X'' is --O--, --S--, --CO--, --CO--O--,
--O--CO--, --O--CO--O--, --CO--N(R.sup.0)--, --N(R.sup.0)--CO--,
--N(R.sup.0)--CO--N(R.sup.0)--, --OCH.sub.2--, --CH.sub.2O--,
--SCH.sub.2--, --CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--,
--CF.sub.2S--, --SCF.sub.2--, --CF.sub.2CH.sub.2--,
--CH.sub.2CF.sub.2--, --CF.sub.2CF.sub.2--, --CH.dbd.N--,
--N.dbd.CH--, --N.dbd.N--, --CH.dbd.CR.sup.0--,
--CY.sup.2.dbd.CY.sup.3--, --C.ident.C--, --CH.dbd.CH--CO--O--,
--O--CO--CH.dbd.CH-- or a single bond, in which R.sup.0 is hydrogen
or alkyl having 1 to 12 carbons, and Y.sup.2 and Y.sup.3 are
independently hydrogen, fluorine, chlorine or --CN. Preferred X''
is --O--, --S--, --CO--, --COO--, --OCO--, --O--COO--,
--CO--NR.sup.0--, --NR.sup.0--CO--, --NR.sup.0--CO--NR.sup.0-- or a
single bond. Sp.sup.5 is >CH--, >CR.sup.11--, >N-- or
>C<. More specifically, Sp.sup.5 in formula (A2) means
>CH--, >CR.sup.11-- or >N--, and Sp.sup.5 in formula (A3)
means >C<.
Preferred Sp'' is --(CH.sub.2).sub.p1--,
--(CH.sub.2CH.sub.2O).sub.q1--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--S--CH.sub.2CH.sub.2-- or
--CH.sub.2CH.sub.2--NHCH.sub.2CH.sub.2--, in which p1 is an integer
from 1 to 12 and q1 is an integer from 1 to 3. Preferred group
(-Sp''-X''--) is --(CH.sub.2).sub.p1--, --(CH.sub.2).sub.p1--O--,
--(CH.sub.2).sub.p1--O--CO-- or --(CH.sub.2).sub.p1--O--CO--O--, in
which p1 and q1 have the meaning described above. Further preferred
group Sp'' is ethylene, propylene, butylene, pentylene, hexylene,
heptylene, octylene, nonylene, decylene, undecylene, dodecylene,
octadecylene, ethyleneoxyethylene, methyleneoxybutylene,
ethylenethioethylene, ethylene-N-methyliminoethylene,
1-methylalkylene, ethenylene, propenylene and butenylene.
X.sup.3 is --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2,
--OR.sup.11, --OH, --COOH, --SH, --SR.sup.11,
##STR00031## in which R.sup.11 is alkyl having 1 to 15 carbons, and
in the alkyl, at least one piece of --CH.sub.2-- may be replaced by
--C.ident.C--, --CH.dbd.CH--, --COO--, --OCO--, --CO-- or --O--,
and in the groups, at least one hydrogen may be replaced by
fluorine or chlorine, and R.sup.0 is hydrogen or alkyl having 1 to
12 carbons.
X.sup.4 is --O--, --CO--, --NH--, --NR.sup.11--, --S-- or a single
bond, and Z.sup.6 is alkylene having 1 to 15 carbons, an alicyclic
group having 5 to 6 carbons or a combination thereof, and in the
groups, at least one hydrogen may be replaced by --OH, --OR.sup.11,
--COOH, --NH.sub.2, --NHR.sup.11, --N(R.sup.11).sub.2, fluorine or
chlorine, in which R.sup.11 has the meaning described above. Then,
j is 0, 1, 2 or 3.
Particularly preferred nitrogen-containing group R.sup.5 is
--NH.sub.2, --NH--(CH.sub.2).sub.n3H, --(CH.sub.2).sub.n--NH.sub.2,
--(CH.sub.2).sub.n--NH--(CH.sub.2).sub.n3H,
--NH--(CH.sub.2).sub.n--NH.sub.2,
--NH--(CH.sub.2).sub.n--NH--(CH.sub.2).sub.n3H,
--(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--NH.sub.2,
(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--NH--(CH.sub.2).sub.n3H,
--O--(CH.sub.2).sub.n--NH.sub.2,
--(CH.sub.2).sub.n1--O--(CH.sub.2).sub.n--NH.sub.2,
--(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--OH,
--O--(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--NH.sub.2,
--O--(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--OH or
--(CH.sub.2).sub.n1--NH--(CH.sub.2).sub.n2--NH--(CH.sub.2).sub.n3H,
in which n, n1, n2 and n3 are independently an integer from 1 to
12, and are preferably 1, 2, 3 or 4.
Particularly preferred nitrogen-noncontaining group R.sup.5 is
--OH, --(CH.sub.2).sub.n--OH, --O--(CH.sub.2).sub.n--OH,
--[O--(CH.sub.2).sub.n1-].sub.n2--OH, --COOH,
--(CH.sub.2).sub.n--COOH, --O--(CH.sub.2).sub.n--COOH or
--[O--(CH.sub.2).sub.n1-].sub.n2--COOH, in which n, n1 and n2 are
independently an integer from 1 to 12, and are preferably 1, 2, 3
or 4.
From a viewpoint of high solubility in the liquid crystal
composition, R.sup.5 is particularly preferably --OH or --NH.sub.2.
Then, --OH has high anchor force, and therefore is further
preferred to --O--, --CO-- or --COO--. A group containing a
plurality of hetero atoms (nitrogen, oxygen) is particularly
preferred. A compound having such a polar group is effective even
at a low concentration.
In formula (6), MES is a mesogen group having at least one ring.
The mesogen group is known by those skilled in the art. The mesogen
group means a moiety contributing to formation of a liquid crystal
phase when the compound has the liquid crystal phase (mesophase).
Preferred examples of compound (6) include compound (6-1).
In formula (6-1), ring G and ring I are independently an aromatic
group having 6 to 25 carbons, a heteroaromatic group having 5 to 25
carbons, an alicyclic group having 3 to 25 carbons or a
heteroalicyclic group having 4 to 25 carbons, and the groups may be
a condensed ring, and in the groups, at least one hydrogen may be
replaced by group T, and in the group, the preferred number of
carbons is 4 to 25. The meaning of group T will be described in a
last part of the present paragraph. Preferred ring G or ring I is
1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (in the
three groups, at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--)), 1,4-cyclohexylene (in the group,
at least one piece of --CH.sub.2-- may be replaced by --O-- or
--S--), 3,3'-bicyclobutylidene, 1,4-cyclohexenylene,
bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl,
spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl,
decahydronaphthalene-2,6-diyl,
1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl,
octahydro-4,7-methanoindan-2,5-diyl or
perhydrocyclopenta[a]phenanthrene-3,17-diyl (particularly,
gonane-3,17-diyl), and in the groups, at least one hydrogen may be
replaced by group T, in which group T is --OH,
--(CH.sub.2).sub.i--OH, halogen, --CN, --NO.sub.2, --NCO, --NCS,
--OCN, --SCN, --C(.dbd.O)N(R.sup.0).sub.2, --C(.dbd.O)R.sup.0,
--N(R.sup.0).sub.2, --(CH.sub.2).sub.i--N(R.sup.0).sub.2, aryl or
heteroaryl having 6 to 20 carbons, alkyl having 1 to 25 carbons,
alkoxy having 1 to 25 carbons, alkylcarbonyl having 2 to 25
carbons, alkoxycarbonyl having 2 to 25 carbons, alkylcarbonyloxy or
alkoxycarbonyloxy having 2 to 25 carbons, and in the groups, at
least one hydrogen may be replaced by fluorine or chlorine, in
which R.sup.0 is hydrogen or alkyl having 1 to 12 carbons, and i is
1, 2, 3 or 4.
Z.sup.5 is a single bond, --O--, --S--, --CO--, --CO--O--, --OCO--,
--O--CO--O--, --OCH.sub.2--, --CH.sub.2O--, --SCH.sub.2--,
--CH.sub.2S--, --CF.sub.2O--, --OCF.sub.2--, --CF.sub.2S--,
--SCF.sub.2--, --(CH.sub.2).sub.i--, --CF.sub.2CH.sub.2--,
--CH.sub.2CF.sub.2--, --(CF.sub.2).sub.i--, --CH.dbd.CH--,
--CF.dbd.CF--, --C.ident.C--, --CH.dbd.CH--COO--,
--OCO--CH.dbd.CH-- or --C(R.sup.0).sub.2--. R.sup.0 is hydrogen or
alkyl having 1 to 12 carbons, and i is 1, 2, 3 or 4. Preferred
Z.sup.5 is a single bond.
R.sup.5 is alkyl having 1 to 25 carbons, and in the alkyl, at least
one piece of --CH.sub.2-- may be replaced by --NR.sup.0--, --O--,
--S--, --CO--, --COO--, --OCO--, --OCOO-- or cycloalkylene having 3
to 8 carbons, in which R.sup.0 is hydrogen or alkyl having 1 to 12
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and at least one hydrogen may be
replaced by fluorine or chlorine, in which R.sup.5 has at least one
of an oxygen atom having an OH structure, a sulfur atom having an
SH structure, and a nitrogen atom having a primary, secondary or
tertiary amine structure. Preferred R.sup.5 has at least one piece
of >NH, --OH or --SH. R.sup.6 is hydrogen, halogen, alkyl having
1 to 25 carbons, and in the alkyl, at least one piece of
--CH.sub.2-- may be replaced by --NR.sup.0--, --O--, --S--, --CO--,
--CO--O--, --O--CO--, --O--CO--O-- or cycloalkylene having 3 to 8
carbons, and at least one tertiary carbon (>CH--) may be
replaced by nitrogen (>N--), and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine, in which R.sup.0
is hydrogen or alkyl having 1 to 12 carbons. Preferred R.sup.6 is
alkyl.
An aromatic group refers to aryl or substituted aryl. A
heteroaromatic group refers to heteroaryl or substituted
heteroaryl. Heteroaryl represents an aromatic group containing at
least one hetero atom. Aryl and heteroaryl may be either monocyclic
or polycyclic. More specifically, the above groups have at least
one ring, and the ring may be condensed (for example, naphthyl),
and the two rings may be linked by a covalent bond (for example,
biphenyl), or may have a combination of a condensed ring and a
linkage. Preferred heteroaryl contains at least one hetero atom
selected from the group of nitrogen, oxygen, sulfur and
phosphorus.
Preferred aryl or heteroaryl may have 6 to 25 carbons, and may be a
five-membered ring, a six-membered ring or a seven membered-ring.
Preferred aryl or heteroaryl may be monocyclic, bicyclic or
tricyclic. The above groups may be a condensed ring, or may be
substituted.
Preferred aryl is a monovalent group derived therefrom by
eliminating one hydrogen from benzene, biphenyl, terphenyl,
[1,1':3',1'']terphenyl, naphthalene, anthracene, binaphtyl,
phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene,
pentacene, benzopyrene, fluorene, indene, indeno fluorene and
spirobifluorene.
Preferred heteroaryl is a monovalent group derived therefrom by
eliminating one hydrogen from a five-membered ring compound such as
pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole,
tetrazole, furan, thiophene, selenophene, oxazole, isoxazole,
1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole,
1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,
1,2,4-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole, or from
a six-membered ring compound such as pyridine, pyridazine,
pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine,
1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine and
1,2,3,5-tetrazine.
Another preferred heteroaryl is a monovalent group derived
therefrom by eliminating one hydrogen from a condensed ring
compound such as indole, isoindole, indolizine, indazole,
benzimidazole, benzotriazol, purine, naphthimidazole,
phenanthoraimidazole, pyridaimidazole, pyrazineimidazole,
quinoxalineimidazole, benzoxazole, naphthaxazole, antroxazole,
phenanthroxazole, isoxazole, benzothiazole, benzofuran,
isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine,
benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,
benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzo
pyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine,
azacarbazole, benzocarboline, phenanthridine, phenanthroline,
thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene,
isobenzothiophene, dibenzothiophene and benzothiadiazothiophene.
Preferred heteroaryl is also a monovalent group derived therefrom
by eliminating one hydrogen from a ring obtained by combining two
groups selected from the five-membered ring, the six-membered ring
and the condensed ring. The heteroaryl may be replaced by alkyl,
alkoxy, thioalkyl, fluorine, fluoroalkyl, aryl or heteroaryl.
An alicyclic group and a heteroalicyclic group may be saturated or
may be unsaturated. More specifically, the above groups may have
only a single bond or may have a combination of a single bond and a
multiple bond. A saturated ring is preferred to an unsaturated
ring. A preferred heteroalicyclic group contains at least one
hetero atom selected from nitrogen, oxygen, sulfur and
phosphorus.
An alicyclic group and a heteroalicyclic group may have one ring,
or a plurality of rings. Preferred examples of the groups include a
monocyclic ring, a bicyclic ring or a tricyclic ring each having 3
to 25 carbons, and the groups may be a condensed ring or may be
substituted. Preferred examples of the groups include a
five-membered ring, a six-membered ring, a seven membered-ring or
an eight membered-ring, and in the groups, at least one carbon may
be replaced by silicon, and at least one piece of >CH-- may be
replaced by >N--, and at least one piece of --CH.sub.2-- may be
replaced by --O-- or --S--.
A preferred alicyclic group and heteroalicyclic group is a divalent
group derived therefrom by eliminating two hydrogens from a
five-membered ring such as cyclopentane, tetrahydrofuran,
tetrahydrothiofuran and pyrrolidine; a six-membered ring such as
cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran,
1,3-dioxane, 1,3-dithian and piperidine; a seven membered-ring such
as cycloheptane; and a condensed ring such as
tetrahydronaphthalene, decahydronaphthalene, indan,
bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, spiro[3.3]heptane and
octahydro-4,7-methanoindan.
Then, h is 0, 1, 2, 3, 4 or 5.
In formula (7), R.sup.4 is alkyl having 4 to 20 carbons, and in the
alkyl, at least one piece of --CH.sub.2-- may be replaced by
--CH.dbd.CH--, --CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or
cycloalkylene having 3 to 8 carbons, and at least one hydrogen may
be replaced by fluorine or chlorine. Then, g is 1 or 2, and is
preferably 1.
Preferred R.sup.4 is alkyl having 4 to 20 carbons. Further
preferred R.sup.4 is alkyl having 6 to 18 carbons. At least one
piece of --CH.sub.2-- may be replaced by --CH.dbd.CH--,
--CF.dbd.CH--, --CH.dbd.CF--, --C.ident.C-- or --O--, and at least
one hydrogen may be replaced by fluorine or chlorine.
Particularly preferred compound (6-1) is selected from the
compounds described below.
##STR00032## ##STR00033## ##STR00034## ##STR00035##
##STR00036##
In formula (6-1-1-1) to formula (6-1-4-4), R.sup.6 is alkyl having
1 to 8 carbons or fluorine.
Particularly preferred compound (7-1) is selected from compound
(7-1-1-1) to compound (7-1-29-1) described below.
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044##
In formula (8), P.sup.1, P.sup.2 and P.sup.3 are independently a
polymerizable group. Preferred P.sup.1, P.sup.2 or P.sup.3 is a
polymerizable group selected from the group of groups represented
by formula (P-1) to formula (P-5). Further preferred P.sup.1,
P.sup.2 or P.sup.3 is a group represented by formula (P-1), formula
(P-2) or formula (P-3). Particularly preferred P.sup.1, P.sup.2 or
P.sup.3 is a group represented by formula (P-1) or formula (P-2).
Most preferred P.sup.1, P.sup.2 or P.sup.3 is a group represented
by formula (P-1). A preferred group represented by formula (P-1) is
--OCO--CH.dbd.CH.sub.2 or --OCO--C(CH.sub.3).dbd.CH.sub.2. A wavy
line in formula (P-1) to formula (P-5) shows a site to which
bonding is made.
##STR00045##
In formula (P-1) to formula (P-5), M.sup.1, M.sup.2 and M.sup.3 are
independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or
alkyl having 1 to 5 carbons in which at least one hydrogen is
replaced by fluorine or chlorine. Preferred M.sup.1, M.sup.2 or
M.sup.3 is hydrogen or methyl for increasing reactivity. Further
preferred M.sup.1 is hydrogen or methyl, and further preferred
M.sup.2 or M.sup.3 is hydrogen.
Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or
alkylene having 1 to 10 carbons, and in the alkylene, at least one
piece of --CH.sub.2-- may be replaced by --O--, --COO--, --OCO-- or
--OCOO--, and at least one piece of --CH.sub.2CH.sub.2-- may be
replaced by --CH.dbd.CH-- or --C.ident.C--, and in the groups, at
least one hydrogen may be replaced by fluorine or chlorine.
Preferred Sp.sup.1, Sp.sup.2 or Sp.sup.3 is a single bond,
--CH.sub.2CH.sub.2--, --CH.sub.2O--, --OCH.sub.2--, --COO--,
--OCO--, --CO--CH.dbd.CH-- or --CH.dbd.CH--CO--. Further preferred
Sp.sup.1, Sp.sup.2 or Sp.sup.3 is a single bond, in which, when
ring A and ring C are phenyl, Sp.sup.1 and Sp.sup.3 are a single
bond.
Ring A and ring C are independently cyclohexyl, cyclohexenyl,
phenyl, l-naphthyl, 2-naphthyl, tetrahydropyran-2-yl,
1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and in the
rings, at least one hydrogen may be replaced by fluorine, chlorine,
alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or
alkyl having 1 to 12 carbons in which at least one hydrogen is
replaced by fluorine or chlorine. Preferred ring A or ring C is
phenyl. Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene,
1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl,
naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl,
naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl,
naphthalene-2,6-diyl, naphthalene-2,7-diyl,
tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl
or pyridine-2,5-diyl, and in the rings, at least one hydrogen may
be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons,
alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in
which at least one hydrogen is replaced by fluorine or chlorine.
Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.
Z.sup.1 and Z.sup.2 are independently a single bond or alkylene
having 1 to 10 carbons, and in the alkylene, at least one piece of
--CH.sub.2-- may be replaced by --O--, --CO--, --COO-- or --OCO--,
and at least one piece of --CH.sub.2CH.sub.2-- may be replaced by
--CH.dbd.CH--, --C(CH.sub.3).dbd.CH--, --CH.dbd.C(CH.sub.3)-- or
--C(CH.sub.3).dbd.C(CH.sub.3)--, and in the groups, at least one
hydrogen may be replaced by fluorine or chlorine. Preferred Z.sup.1
or Z.sup.2 is a single bond, --CH.sub.2CH.sub.2--, --CH.sub.2O--,
--OCH.sub.2--, --COO-- or --OCO--. Further preferred Z.sup.1 or
Z.sup.2 is a single bond.
Then, a is 0, 1 or 2. Preferred a is 0 or 1. Then, b, c, and d are
independently 0, 1, 2, 3 or 4, and a sum of b, c and d is 1 or
more. Preferred b, c or d is 1 or 2.
Fifth, the preferred component compounds will be described.
Preferred compound (1) includes compound (1-1) to compound (1-14)
described in item 2. In the compounds, at least one of the first
components preferably includes compound (1-3), compound (1-4),
compound (1-7), compound (1-9), compound (1-10) or compound (1-12).
At least two of the first components preferably include a
combination of compound (1-3) and compound (1-4), a combination of
compound (1-3) and compound (1-7), a combination of compound (1-3)
and compound (1-10), a combination of compound (1-7) and compound
(1-10) or a combination of compound (1-9) and compound (1-10).
Preferred compound (3) includes compound (3-1) to compound (3-12)
described in item 5. In the compounds, at least one of the third
components preferably include compound (3-2), compound (3-4),
compound (3-5), compound (3-6) or compound (3-12).
Preferred compound (4) includes compound (4-1) to compound (4-16)
described in item 8. In the compounds, at least one of the fourth
components preferably includes compound (4-4), compound (4-8),
compound (4-9), compound (4-11), compound (4-12), compound (4-13)
or compound (4-16). At least two of the fourth components
preferably include a combination of compound (4-9) and compound
(4-12), a combination of compound (4-11) and compound (4-12), a
combination of compound (4-12) and compound (4-13) or a combination
of compound (4-12) and compound (4-16).
Preferred compound (5) includes compound (5-1) to compound (5-21)
described in item 11. In the compounds, at least one of the fifth
components preferably includes compound (5-1), compound (5-4),
compound (5-5), compound (5-7), compound (5-10) or compound (5-15).
At least two of the fifth components preferably include a
combination of compound (5-1) and compound (5-7), a combination of
compound (5-1) and compound (5-15), a combination of compound (5-4)
and compound (5-7), a combination of compound (5-4) and compound
(5-15), a combination of compound (5-5) and compound (5-7) or a
combination of compound (5-5) and compound (5-10).
Preferred compound (6) includes compound (6-1) described in item
15. Further preferred compound (6) includes compound (6-1-1) to
compound (6-1-4) described in item 18. Preferred compound (7)
includes compound (7-1) described in item 16. Further preferred
compound (7) includes compound (7-1-1) to compound (7-1-29)
described in item 19. In general, compound (6) is preferred to
compound (7).
Preferred compound (8) includes compound (8-1) to compound (8-28)
described in item 23. Further preferred compound (8) includes
compound (8-1), compound (8-2), compound (8-3), compound (8-4),
compound (8-5), compound (8-6), compound (8-7), compound (8-18),
compound (8-20), compound (8-23), compound (8-24), compound (8-25)
and compound (8-26). Particularly preferred compound (8) includes
compound (8-2), compound (8-3), compound (8-4) and compound
(8-18).
Sixth, the additive that may be added to the composition will be
described. Such an additive includes the optically active compound,
the antioxidant, the ultraviolet light absorber, the dye, the
antifoaming agent, the polymerizable compound, the polymerization
initiator, the polymerization inhibitor, the polar compound or the
like. The optically active compound is added to the composition for
the purpose of inducing a helical structure in the liquid crystal
molecule to give a twist angle. Examples of such a compound include
compound (9-1) to compound (9-5). A preferred proportion of the
optically active compound is about 5% by weight or less. A further
preferred proportion is in the range of about 0.01% by weight to
about 2% by weight.
##STR00046##
The antioxidant is added to the composition for preventing a
decrease in the specific resistance caused by heating in air, or
for maintaining a large voltage holding ratio at room temperature
and also at the temperature close to the maximum temperature even
after the device has been used for a long period of time. Preferred
examples of the antioxidant include compound (10) where n is an
integer from 1 to 9.
##STR00047##
In compound (10), preferred n is 1, 3, 5, 7 or 9. Further preferred
n is 7. Compound (10) where n is 7 has small volatility, and
therefore is effective in maintaining a large voltage holding ratio
at room temperature and also at the temperature close to the
maximum temperature even after the device has been used for a long
period of time. A preferred proportion of the antioxidant is about
50 ppm or more for achieving an effect thereof, and about 600 ppm
or less for avoiding a decrease in the maximum temperature or an
increase in the minimum temperature. A further preferred proportion
is in the range of about 100 ppm to about 300 ppm.
Preferred examples of the ultraviolet light absorber include a
benzophenone derivative, a benzoate derivative and a triazole
derivative. A light stabilizer such as an amine having steric
hindrance is also preferred. A preferred proportion of the absorber
or the stabilizer is about 50 ppm or more for achieving an effect
thereof, and about 10,000 ppm or less for avoiding the decrease in
the maximum temperature or avoiding the increase in the minimum
temperature. A further preferred proportion is in the range of
about 100 ppm to about 10,000 ppm.
A dichroic dye such as an azo dye or an anthraquinone dye is added
to the composition to be adapted for a device having a guest host
(GH) mode. A preferred proportion of the dye is in the range of
about 0.01% by weight to about 10% by weight. The antifoaming agent
such as dimethyl silicone oil or methyl phenyl silicone oil is
added to the composition for preventing foam formation. A preferred
proportion of the antifoaming agent is about 1 ppm or more for
achieving an effect thereof, and about 1,000 ppm or less for
preventing poor display. A further preferred proportion is in the
range of about 1 ppm to about 500 ppm.
The polymerizable compound is used to be adapted for a polymer
sustained alignment (PSA) mode device. Compound (8) is suitable for
the above purpose. Any other polymerizable compound that is
different from compound (8) may be added to the composition
together with compound (8). Preferred examples of any other
polymerizable compounds include acrylate, methacrylate, a vinyl
compound, a vinyloxy compound, propenyl ether, an epoxy compound
(oxirane, oxetane) and a vinyl ketone compound. Further preferred
examples include acrylate or methacrylate. A preferred proportion
of compound (8) is about 10% by weight or more based on the total
weight of the polymerizable compound. A further preferred
proportion is about 50% by weight or more. A particularly preferred
proportion is about 80% by weight or more. A particularly preferred
proportion is also 100% of the weight. Reactivity of a
polymerizable compound and a pretilt angle of a liquid crystal
molecule can be adjusted by changing a kind of compound (8), or by
combining any other polymerizable compounds with compound (8) at a
suitable ratio. A short response time of the device can be achieved
by optimizing the pretilt angle. Because the alignment of the
liquid crystal molecule is stabilized, a large contrast ratio and a
long service life can be achieved.
A polymerizable compound such as compound (8) is polymerized by
irradiation with ultraviolet light. The polymerizable compound may
be polymerized in the presence of a suitable initiator such as a
photopolymerization initiator. Suitable conditions for
polymerization, suitable types of the initiator and suitable
amounts thereof are known to those skilled in the art and are
described in literature. For example, Irgacure 651 (registered
trademark; BASF), Irgacure 184 (registered trademark; BASF) or
Darocur 1173 (registered trademark; BASF), each being a
photoinitiator, is suitable for radical polymerization. A preferred
proportion of the photopolymerization initiator is in the range of
about 0.1% by weight to about 5% by weight based on the total
weight of the polymerizable compound. A further preferred
proportion is in the range of about 1% by weight to about 3% by
weight based thereon.
Upon storing the polymerizable compound such as compound (8), the
polymerization inhibitor may be added thereto for preventing
polymerization. The polymerizable compound is ordinarily added to
the composition without removing the polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, a
hydroquinone derivative such as methylhydroquinone,
4-t-butylcatechol, 4-methoxyphenol and phenothiazine.
Seventh, the methods for synthesizing the component compounds will
be described. The compounds can be prepared according to known
methods. Examples of the synthetic methods are described. Compound
(1-4) and compound (1-10) are prepared by the method described in
JP H10-251186 A. Compound (2) is prepared by the method described
in JP S59-176221 A. Compound (3-12) is prepared by the method
described in JP H2-237949 A. Compound (4-4) and compound (4-8) are
prepared by the method described in JP H2-233626 A. Compound (5-1)
and compound (5-7) are prepared by the method described in JP
H2-503441 A. Compound (6-1) is prepared by the method described in
WO 2012/038026 A. Some of compound (7) are commercially available.
Compound (8-17) is prepared by the method described in JP H7-101900
A. Compound in which n is 1 in formula (10) can be obtained from
Aldrich (Sigma-Aldrich Corporation). Compounds (10) where n is 7 is
prepared by the method described in U.S. Pat. No. 3,660,505 B.
Any compounds whose synthetic methods are not described above can
be prepared according to the methods described in books such as
Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions
(John Wiley & Sons, Inc.), Comprehensive Organic Synthesis
(Pergamon Press) and New Experimental Chemistry Course (Shin Jikken
Kagaku Koza in Japanese) (Maruzen Co., Ltd.). The composition is
prepared according to publicly known methods using the thus
obtained compounds. For example, the component compounds are mixed
and dissolved in each other by heating.
Last, the application of the composition will be described. Most of
the composition has a minimum temperature of about -10.degree. C.
or lower, a maximum temperature of about 70.degree. C. or higher,
and optical anisotropy in the range of about 0.07 to about 0.20.
The composition having optical anisotropy in the range of about
0.08 to about 0.25 may be prepared by controlling the proportion of
the component compounds or by mixing any other liquid crystal
compound. Further, the composition having optical anisotropy in the
range of about 0.10 to about 0.30 may be prepared by trial and
error. A device including the composition has the large voltage
holding ratio. The composition is suitable for use in the AM
device. The composition is particularly suitable for use in a
transmissive AM device. The composition can be used as the
composition having the nematic phase, and as the optically active
composition by adding the optically active compound.
The composition can be used for the AM device. The composition can
also be used for a PM device. The composition can also be used for
an AM device and a PM device each having a mode such as the PC
mode, the TN mode, the STN mode, the ECB mode, the OCB mode, the
IPS mode, the FFS mode, the VA mode and the FPA mode. Use for the
AM device having the TN mode, the OCB mode, the IPS mode or the FFS
mode is particularly preferred. In the AM device having the IPS
mode or the FFS mode, when no voltage is applied, the alignment of
liquid crystal molecules may be parallel to a glass substrate, or
may be perpendicular thereto. The above devices may be a reflective
type, a transmissive type, or a transflective type. Use for the
transmissive device is preferred. The composition can also be used
for an amorphous silicon-TFT device or a polycrystal silicon-TFT
device. The composition can also be used for a nematic curvilinear
aligned phase (NCAP) device prepared by microencapsulating the
composition, or for a polymer dispersed (PD) device in which a
three-dimensional network-polymer is formed in the composition.
One example of a conventional method of producing the polymer
sustained alignment mode device is as described below. A device
having two substrates called an array substrate and a color filter
substrate is assembled. The substrates each include an alignment
film. At least one of the substrates includes an electrode layer. A
liquid crystal compound is mixed to prepare a liquid crystal
composition. A polymerizable compound is added to the composition.
An additive may be further added thereto when necessary. The
composition is injected into the device. The device is irradiated
with light while voltage is applied to the device. Ultraviolet
light is preferred. A polymerizable compound is polymerized by
irradiation with light. A composition containing a polymer is
formed by the polymerization. The polymer sustained alignment mode
device is produced by such a procedure.
In the above procedure, when voltage is applied, liquid crystal
molecules are aligned by action of the alignment film and an
electric field. Molecules of the polymerizable compound are also
aligned according to the above alignment. The polymerizable
compound is polymerized by ultraviolet light in the above state,
and therefore a polymer in which the alignment is maintained is
formed. A response time of the device is shortened by an effect of
the polymer. Image persistence is caused by poor operation of the
liquid crystal molecule, and therefore is also simultaneously
improved by the effect of the polymer. In addition, the
polymerizable compound in the composition may be polymerized in
advance, and the composition may be arranged between the substrates
of the liquid crystal display device.
One example of a method of producing a device having no alignment
film is as described below. A device having two substrates called
an array substrate and a color filter substrate is prepared. The
substrates each include no alignment film. At least one of the
substrates includes an electrode layer. A liquid crystal compound
is mixed to prepare a liquid crystal composition. A polymerizable
compound and a polar compound are added to the composition. An
additive may be further added thereto when necessary. The
composition is injected into the device. The device is irradiated
with light while voltage is applied to the device. Ultraviolet
light is preferred. A polymerizable compound is polymerized by
irradiation with light. A layer of the composition containing a
polymer and a polar compound is formed on the substrate by the
polymerization.
In the above procedure, because a polar group interacts with a
substrate surface, the polar compound is arranged on the substrate.
Liquid crystal molecules are arranged according to the above
arrangement. When voltage is applied, the alignment of the liquid
crystal molecules is further promoted and the polymerizable
compound is also aligned according to the above alignment. The
polymerizable compound is polymerized by ultraviolet light in the
above state, and therefore a polymer in which the alignment is
maintained is formed. The alignment of the liquid crystal molecules
is additionally stabilized by an effect of the polymer, and a
response time of the device is shortened. Image persistence is
caused by poor operation of the liquid crystal molecule, and
therefore is also simultaneously improved by the effect of the
polymer.
EXAMPLES
The invention will be described in greater detail by way of
Examples. The invention is not limited by the Examples. The
invention includes a mixture of composition M1 and composition M2.
The invention also includes a mixture prepared by mixing at least
two of compositions in Examples. A compound prepared was identified
by methods such as an NMR analysis. Characteristics of the
compound, the composition and a device were measured by methods
described below.
NMR analysis: For measurement, DRX-500 made by Bruker BioSpin
Corporation was used. In .sup.1H-NMR measurement, a sample was
dissolved in a deuterated solvent such as CDCl.sub.3, and
measurement was carried out under conditions of room temperature,
500 MHz and 16 times of accumulation. Tetramethylsilane was used as
an internal standard. In .sup.19F-NMR measurement, CFCl.sub.3 was
used as an internal standard, and measurement was carried out under
conditions of 24 times of accumulation. In explaining nuclear
magnetic resonance spectra obtained, s, d, t, q, quin, sex and m
stand for a singlet, a doublet, a triplet, a quartet, a quintet, a
sextet and a multiplet, and br being broad, respectively.
Gas chromatographic analysis: For measurement, GC-14B Gas
Chromatograph made by Shimadzu Corporation was used. A carrier gas
was helium (2 mL/min). A sample vaporizing chamber and a detector
(FID) were set to 280.degree. C. and 300.degree. C., respectively.
A capillary column DB-1 (length 30 m, bore 0.32 mm, film thickness
0.25 .mu.m; dimethylpolysiloxane as a stationary phase, non-polar)
made by Agilent Technologies, Inc. was used for separation of
component compounds. After the column was kept at 200.degree. C.
for 2 minutes, the column was heated to 280.degree. C. at a rate of
5.degree. C. per minute. A sample was prepared in an acetone
solution (0.1% by weight), and then 1 microliter of the solution
was injected into the sample vaporizing chamber. A recorder was
C-R5A Chromatopac made by Shimadzu Corporation or the equivalent
thereof. The resulting gas chromatogram showed a retention time of
a peak and a peak area corresponding to each of the component
compounds.
As a solvent for diluting the sample, chloroform, hexane or the
like may also be used. The following capillary columns may also be
used for separating component compounds: HP-1 (length 30 m, bore
0.32 mm, film thickness 0.25 .mu.m) made by Agilent Technologies,
Inc., Rtx-1 (length 30 m, bore 0.32 mm, film thickness 0.25 .mu.m)
made by Restek Corporation and BP-1 (length 30 m, bore 0.32 mm,
film thickness 0.25 .mu.m) made by SGE International Pty. Ltd. A
capillary column CBP1-M50-025 (length 50 m, bore 0.25 mm, film
thickness 0.25 .mu.m) made by Shimadzu Corporation may also be used
for the purpose of preventing an overlap of peaks of the
compounds.
A proportion of liquid crystal compounds contained in the
composition may be calculated by a method as described below. A
mixture of liquid crystal compounds is analyzed by gas
chromatograph (FID). An area ratio of each peak in the gas
chromatogram corresponds to the proportion of the liquid crystal
compound. When the capillary columns described above were used, a
correction coefficient of each of the liquid crystal compounds may
be regarded as 1. Accordingly, the proportion (% by weight) of the
liquid crystal compounds can be calculated from the area ratio of
each peak.
Sample for measurement: When characteristics of the composition and
the device were measured, the composition was used as was. Upon
measuring characteristics of a compound, a sample for measurement
was prepared by mixing the compound (15% by weight) with a base
liquid crystal (85% by weight). Values of characteristics of the
compound were calculated, according to an extrapolation method,
using values obtained by measurement. (Extrapolated
value)={(measured value of a sample for
measurement)-0.85.times.(measured value of a base liquid
crystal)}/0.15. When a smectic phase (or crystals) precipitates at
the ratio thereof at 25.degree. C., a ratio of the compound to the
base liquid crystal was changed step by step in the order of (10%
by weight: 90% by weight), (5% by weight: 95% by weight) and (1% by
weight: 99% by weight). Values of maximum temperature, optical
anisotropy, viscosity and dielectric anisotropy with regard to the
compound were determined according to the extrapolation method.
A base liquid crystal described below was used. A proportion of the
component compound was expressed in terms of weight percent (% by
weight).
##STR00048##
Measuring method: Physical properties were measured according to
the methods described below. Most of the methods are described in
the Standard of Japan Electronics and Information Technology
Industries Association (hereinafter, abbreviated as JEITA)
discussed and established in JEITA (JEITA ED-2521B). A modification
of the methods was also used. No thin film transistor (TFT) was
attached to a TN device used for measurement.
(1) Maximum temperature of a nematic phase (NI; .degree. C.): A
sample was placed on a hot plate in a melting point apparatus
equipped with a polarizing microscope, and heated at a rate of
1.degree. C. per minute. Temperature when part of the sample began
to change from a nematic phase to an isotropic liquid was measured.
A higher limit of the temperature range of the nematic phase may be
occasionally abbreviated as "maximum temperature."
(2) Minimum temperature of a nematic phase (T.sub.c; .degree. C.):
Samples each having a nematic phase were put in glass vials and
kept in freezers at temperatures of 0.degree. C., -10.degree. C.,
-20.degree. C., -30.degree. C. and -40.degree. C. for 10 days, and
then liquid crystal phases were observed. For example, when the
sample maintained in the nematic phase at -20.degree. C. and
changed to crystals or a smectic phase at -30.degree. C., Tc of the
sample was expressed as Tc<-20.degree. C. A lower limit of the
temperature range of the nematic phase may be occasionally
abbreviated as "minimum temperature."
(3) Viscosity (bulk viscosity; .eta.; measured at 20.degree. C.;
mPas): For measurement, a cone-plate (E type) rotational viscometer
made by Tokyo Keiki Co., Ltd. was used.
(4) Viscosity (rotational viscosity; yl; measured at 25.degree. C.;
mPas): Measurement was carried out according to the method
described in M. Imai et al., Molecular Crystals and Liquid
Crystals, Vol. 259, p. 37 (1995). A sample was put in a TN device
in which a twist angle was 0 degree and a distance (cell gap)
between two glass substrates was 5 micrometers. Voltage was applied
stepwise to the device in the range of 16 V to 19.5 V at an
increment of 0.5 V. After a period of 0.2 second with no voltage
application, voltage was repeatedly applied under conditions of
only one rectangular wave (rectangular pulse; 0.2 second) and no
voltage application (2 seconds). A peak current and a peak time of
a transient current generated by the applied voltage were measured.
A value of rotational viscosity was obtained from the measured
values according to calculating equation (8) on page 40 of the
paper presented by M. Imai et al. Dielectric anisotropy required
for the calculation was measured by a method described in section
(6) described below.
(5) Optical anisotropy (refractive index anisotropy; .DELTA.n;
measured at 25.degree. C.): Measurement was carried out by an Abbe
refractometer with a polarizing plate mounted on an ocular, using
light at a wavelength of 589 nanometers. A surface of a main prism
was rubbed in one direction, and then a sample was added dropwise
onto the main prism. A refractive index (n.parallel.) was measured
when the direction of polarized light was parallel to the direction
of rubbing. A refractive index (n.perp.) was measured when the
direction of polarized light was perpendicular to the direction of
rubbing. A value of optical anisotropy (.DELTA.n) was calculated
from an equation: .DELTA.n=n.parallel.-n.perp..
(6) Dielectric anisotropy (.DELTA..epsilon.; measured at 25.degree.
C.): A sample was put into a TN device in which a distance (cell
gap) between two glass substrates was 9 micrometers and a twist
angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the
device, and after 2 seconds, a dielectric constant
(.epsilon..parallel.) in a major axis direction of the liquid
crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were
applied to the device, and after 2 seconds, a dielectric constant
(.epsilon..perp.) in a minor axis direction of the liquid crystal
molecules was measured. A value of dielectric anisotropy was
calculated from an equation:
.DELTA..epsilon.=.epsilon..parallel.-.epsilon..perp..
(7) Threshold voltage (Vth; measured at 25.degree. C.; V): For
measurement, an LCD-5100 luminance meter made by Otsuka Electronics
Co., Ltd. was used. Alight source was a halogen lamp. A sample was
put in a normally white mode TN device in which a distance (cell
gap) between two glass substrates was 0.45/.DELTA.n (.mu.m) and a
twist angle was 80 degrees. Voltage (32 Hz, rectangular waves) to
be applied to the device was stepwise increased from 0 V to 10 V at
an increment of 0.02 V. On the occasion, the device was irradiated
with light from a direction perpendicular to the device, and an
amount of light transmitted through the device was measured. A
voltage-transmittance curve was prepared, in which a maximum amount
of light corresponds to 100% transmittance and a minimum amount of
light corresponds to 0% transmittance. A threshold voltage is
expressed in terms of voltage at 90% transmittance.
(8) Voltage holding ratio (VHR-1; measured at 25.degree. C.; %): A
TN device used for measurement had a polyimide alignment film, and
a distance (cell gap) between two glass substrates was 5
micrometers. A sample was put in the device, and the device was
sealed with an ultraviolet-curable adhesive. A pulse voltage (60
microseconds at 5 V) was applied to the TN device and the device
was charged. A decaying voltage was measured for 16.7 milliseconds
with a high-speed voltmeter, and area A between a voltage curve and
a horizontal axis in a unit cycle was determined. Area B is an area
without decay. A voltage holding ratio is expressed in terms of a
percentage of area A to area B.
(9) Voltage holding ratio (VHR-2; measured at 80.degree. C.; %): A
voltage holding ratio was measured according to a procedure
identical to the procedure described above except that measurement
was carried out at 80.degree. C. in place of 25.degree. C. The thus
obtained value was expressed in terms of VHR-2.
(10) Voltage holding ratio (VHR-3; measured at 25.degree. C.; %):
Stability to ultraviolet light was evaluated by measuring a voltage
holding ratio after a device was irradiated with ultraviolet light.
A TN device used for measurement had a polyimide alignment film and
a cell gap was 5 micrometers. A sample was injected into the
device, and then the device was irradiated with light for 20
minutes. A light source was an ultra-high-pressure mercury lamp
USH-500D (made by Ushio, Inc.), and a distance between the device
and the light source was 20 centimeters. In measurement of VHR-3, a
decaying voltage was measured for 16.7 milliseconds. A composition
having large VHR-3 has a large stability to ultraviolet light. A
value of VHR-3 is preferably 90% or more, and further preferably
95% or more.
(11) Voltage holding ratio (VHR-4; measured at 25.degree. C.; %):
Stability to heat was evaluated by measuring a voltage holding
ratio after a TN device into which a sample was injected was heated
in a constant-temperature bath at 80.degree. C. for 500 hours. In
measurement of VHR-4, a decaying voltage was measured for 16.7
milliseconds. A composition having large VHR-4 has large stability
to heat.
(12) Response time (T; measured at 25.degree. C.; ms): For
measurement, an LCD-5100 luminance meter made by Otsuka Electronics
Co., Ltd. was used. A light source was a halogen lamp. A low-pass
filter was set to 5 kHz. A sample was put into an FFS device having
no alignment film in which a distance (cell gap) between two glass
substrates was 3.5 micrometers. The device was sealed with an
ultraviolet-curable adhesive. The device was irradiated with
ultraviolet light of 78 mW/cm.sup.2 (405 nm) for 359 seconds (28J)
while a voltage of 30 V was applied to the device. A multi-metal
lamp M04-L41 for ultraviolet curing made by EYE GRAPHICS CO., LTD.
was used for irradiation with ultraviolet light. Rectangular waves
(120 Hz) were applied to the device. On the occasion, the device
was irradiated with light from a direction perpendicular to the
device, and an amount of light transmitted through the device was
measured. The maximum amount of light corresponds to 100%
transmittance and the minimum amount of light corresponds to 0%
transmittance. The maximum voltage of the rectangular wave was set
so as to obtain 90% transmittance. The minimum voltage of the
rectangular wave was set to 2.5V at 0% transmittance. A response
time was expressed in terms of time required for a change from 90%
transmittance to 10% transmittance (fall time; millisecond).
(13) Elastic constant (K; measured at 25.degree. C.; pN): For
measurement, HP4284A LCR Meter made by Yokogawa-Hewlett-Packard Co.
was used. A sample was put into a horizontal alignment device in
which a distance (cell gap) between two glass substrates was 20
micrometers. Voltage of 0 V to 20 V was applied to the device, and
electrostatic capacity and applied voltage were measured. The
measured values of electrostatic capacity (C) and applied voltage
(V) were fitted to equation (2.98) and equation (2.101) on page 75
of "Liquid Crystal Device Handbook" (Ekisho Debaisu Handobukku, in
Japanese; Nikkan Kogyo Shimbun, Ltd.), and values of K11 and K33
were obtained from equation (2.99). Next, K22 was calculated from
equation (3.18) on page 171 by using the values of K11 and K33
obtained previously. Elastic constant K is expressed using a mean
value of the thus determined K11, K22 and K33.
(14) Specific resistance (.rho.; measured at 25.degree. C.;
.OMEGA.cm): Into a vessel equipped with electrodes, 1.0 milliliter
of a sample was injected. A direct current voltage (10 V) was
applied to the vessel, and a direct current after 10 seconds was
measured. Specific resistance was calculated from the following
equation: (specific resistance)={(voltage).times.(electric capacity
of a vessel)}/{(direct current).times.(dielectric constant of
vacuum)}.
(15) Pretilt angle (degree): A spectral ellipsometer M-2000U (made
by J. A. Woollam Co., Inc.) was used for measurement of a pretilt
angle.
(16) Alignment stability (liquid crystal orientation axis
stability): A change in a liquid crystal orientation axis on a side
of an electrode of a liquid crystal display device was evaluated. A
liquid crystal orientation angle o (before) on the side of the
electrode before stress application was measured, and then after
rectangular waves (4.5 V, 60 Hz) were applied to the device for 20
minutes, a short-circuit was formed for 1 second, and liquid
crystal orientation angles o (after) on the side of the electrode
were measured again after 1 second and after 5 minutes,
respectively. From the measured values, changes .DELTA.o (deg.) in
the liquid crystal orientation angles after 1 second and after 5
minutes were calculated, respectively, by using the following
equation: .DELTA.o (deg.)=o (after)-o (before). The above
measurement was carried out with reference to J. Hilfiker, B. Johs,
C. Herzinger, J. F. Elman, E. Montbach, D. Bryant, and P. J. Bos,
Thin Solid Films, 455-456, (2004) 596-600. Smaller .DELTA.o can be
reasonably referred to as being smaller in a change ratio and
better in stability of the liquid crystal orientation axis.
Examples of the composition will be described below. The component
compounds were represented by symbols based on the definition of
the following Table 3. In Table 3, a configuration of
1,4-cyclohexylene is trans. Parenthesized numbers described after
the symbols in Examples represent formulas to which the compounds
belong. A symbol (-) means any other liquid crystal compound. A
proportion (percentage) of the liquid crystal compound is a weight
percent (% by weight) based on the weight of the liquid crystal
composition containing no additives. Finally, characteristic values
of the liquid crystal composition were summarized.
TABLE-US-00003 TABLE 3 Method for Description of Compounds using
Symbols R--(A.sub.1)--Z.sub.1-- . . . --Z.sub.n--(A.sub.n)--R' 1)
Left-terminal Group R-- Symbol C.sub.nH.sub.2n+1-- n-
C.sub.nH.sub.2n+1O-- nO-- C.sub.mH.sub.2m+1OC.sub.nH.sub.2n-- mOn--
CH.sub.2.dbd.CH-- V-- C.sub.nH.sub.2n+1--CH.dbd.CH-- nV--
CH.sub.2.dbd.CH--C.sub.nH.sub.2n-- Vn--
C.sub.mH.sub.2m+1--CH.dbd.CH--C.sub.nH.sub.2n-- mVn--
CF.sub.2.dbd.CH-- VFF-- CF.sub.2.dbd.CH--C.sub.nH.sub.2n-- VFFn--
F--C.sub.nH.sub.2n-- Fn-- 2) Right-terminal Group --R' Symbol
--C.sub.nH.sub.2n+1 -n --OC.sub.nH.sub.2n+1 --On --CH.dbd.CH.sub.2
--V --CH.dbd.CH--C.sub.nH.sub.2n+1 --Vn
--C.sub.nH.sub.2n--CH.dbd.CH.sub.2 --nV
--C.sub.nH.sub.2n--CH.dbd.CH--C.sub.mH.sub.2m+1 --nVm
--CH.dbd.CF.sub.2 --VFF --COOCH.sub.3 --EMe --F --F --Cl --CL
--OCF.sub.3 --OCF3 --CF.sub.3 --CF3 --CN --C 3) Bonding Group
--Z.sub.n-- Symbol --C.sub.2H.sub.4-- 2 --COO-- E --CH.dbd.CH-- V
--C.ident.C-- T --CF.sub.2O-- X --CH.sub.2O-- 1O 4) Ring Structure
--A.sub.n-- Symbol ##STR00049## H ##STR00050## Dh ##STR00051## dh
##STR00052## B ##STR00053## B(F) ##STR00054## B(2F) ##STR00055##
B(F,F) ##STR00056## B(2F,5F) ##STR00057## G ##STR00058## Py
##STR00059## B(2F,3F) ##STR00060## Bm 5) Examples of Description
Example 1 V--HBB-1 ##STR00061## Example 2 5-BB(2F)BBm-2
##STR00062## Example 3 3-BB(F)B(F,F)XB(F,F)--CF3 ##STR00063##
Example 4 3-HHEBH-5 ##STR00064##
Examples of a Device
1. Raw Material
A polar compound and a polymerizable compound were added to liquid
crystal compositions (M1) to (M13), and compositions in Examples 1
to 33 were prepared. The composition was injected into a device
having no alignment film. After the device was irradiated with
ultraviolet light, vertical alignment of liquid crystal molecules
in the device was examined, and the results were summarized in
Table 4. A raw material will be described first. Raw materials
include compositions (M1) to (M13), polar compounds (PC-1) to
(PC-33) and polymerizable compounds (RM-1) to (RM-11), and are
listed up in the above order.
TABLE-US-00004 Composition M1 5-HXB(F,F)-F (1-1) 3% 3-HHXB(F,F)-F
(1-2) 6% 3-BB(F,F)XB(F,F)-F (1-4) 6% 3-BB(2F,3F)XB(F,F)-F (1-4) 4%
3-HHB(F,F)XB(F,F)-F (1-5) 4% 3-HBB(2F,3F)XB(F,F)-F (1-7) 5%
5-BB(F)B(F,F)XB(F)B(F,F)-F (1-14) 2% 3-HH-V (2) 21% 5-HB-O2 (3-1)
5% 3-HHEH-3 (3-3) 3% 3-HBB-2 (3-5) 7% 5-B(F)BB-3 (3-7) 3% 3-HB-CL
(4-1) 3% 3-HHB-OCF3 (4-3) 3% 3-HGB(F,F)-F (4-6) 3% 3-HB(F)B(F,F)-F
(4-9) 5% 3-HHBB(F,F)-F (4-14) 6% 3-HH-V1 (--) 10% 5-BB(2F)BBm-2
(--) 1% Note) A structure of 5-BB(2F)BBm-2 was shown in Example 2
in Table 3. NI = 78.4.degree. C.; Tc < -20.degree. C.; .DELTA.n
= 0.103; .DELTA..epsilon. = 5.8; Vth = 1.90 V; .eta. = 14.0 mPa s;
.gamma.1 = 61.7 mPa s.
TABLE-US-00005 Composition M2 5-HXB(F,F)-F (1-1) 6% 3-HHXB(F,F)-F
(1-2) 6% 2-BB(F)B(F,F)XB(F)-F (1-10) 3% 3-BB(F)B(F,F)XB(F)-F (1-10)
3% 4-BB(F)B(F,F)XB(F)-F (1-10) 4% 3-HH-V (2) 10% 5-HB-O2 (3-1) 7%
4-HHEH-3 (3-3) 3% V2-BB(F)B-1 (3-6) 3% 5-HB-CL (4-1) 5%
V-HB(F)B(F,F)-F (4-9) 5% 3-HHB(F)B(F,F)-F (4-15) 7% 2-HH-5 (--) 8%
3-HH-V1 (--) 7% 4-HH-V (--) 10% 4-HH-V1 (--) 8% 1O1-HBBH-3 (--) 5%
NI = 78.5.degree. C.; Tc < -20.degree. C.; .DELTA.n = 0.095;
.DELTA..epsilon. = 3.4; Vth = 1.50 V; .eta. = 8.4 mPa s; .gamma.1 =
54.2 mPa s.
TABLE-US-00006 Composition M3 3-HHXB(F,F)-F (1-2) 7%
3-BB(F,F)XB(F,F)-F (1-4) 10% 5-HHB(F,F)XB(F,F)-F (1-5) 6%
3-HBB(2F,3F)XB(F,F)-F (1-7) 5% 3-HH-V (2) 20% 3-BB(2F,5F)B-3 (3) 3%
5-HB-O2 (3-1) 5% 3-HHEBH-3 (3-9) 5% 3-HHEBH-5 (3-9) 5%
3-HHEB(F,F)-F (4-5) 5% 5-HBEB(F,F)-F (4-10) 5% 2-HHB(F)B(F,F)-F
(4-15) 3% 2-HH-3 (--) 8% 3-HH-V1 (--) 7% 4-HH-V (--) 6% NI =
90.0.degree. C.; Tc < -20.degree. C.; .DELTA.n = 0.088;
.DELTA..epsilon. = 5.4; Vth = 1.68 V; .eta. = 13.9 mPa s; .gamma.1
= 61.0 mPa s.
TABLE-US-00007 Composition M4 3-BB(F,F)XB(F,F)-F (1-4) 12%
3-HBBXB(F,F)-F (1-7) 3% 3-BB(F)B(F,F)XB(F)-F (1-10) 3%
3-BB(F)B(F,F)XB(F,F)-F (1-10) 3% 4-BB(F)B(F,F)XB(F,F)-F (1-10) 5%
5-BB(F)B(F,F)XB(F,F)-F (1-10) 4% 3-HH-V (2) 25% 5-HB-O2 (3-1) 7%
V-HHB-1 (3-4) 6% V-HBB-2 (3-5) 5% 3-HHBB(F,F)-F (4-14) 5%
4-HHBB(F,F)-F (4-14) 4% 3-HH-5 (--) 6% 2-HH-3 (--) 6% 3-HH-VFF (--)
6% NI = 78.3.degree. C.; Tc < -20.degree. C.; .DELTA.n = 0.107;
.DELTA..epsilon. = 7.0; Vth = 1.55 V; .eta. = 11.6 mPa s; .gamma.1
= 55.6 mPa s.
TABLE-US-00008 Composition M5 3-HHXB(F,F)-F (1-2) 6%
3-BB(F,F)XB(F,F)-F (1-4) 8% 3-BB(F)B(F,F)XB(F,F)-F (1-10) 3%
4-BB(F)B(F,F)XB(F,F)-F (1-10) 6% 5-BB(F)B(F,F)XB(F,F)-F (1-10) 5%
3-HH-V (2) 30% 3-HHB-O1 (3-4) 2% V-HHB-1 (3-4) 5% 2-BB(F)B-3 (3-6)
6% 3-HHBB(F,F)-F (4-14) 5% 4-HHBB(F,F)-F (4-14) 4% 3-HH-V1 (--) 5%
F3-HH-V (--) 15% NI = 82.0.degree. C.; Tc < -20.degree. C.;
.DELTA.n = 0.104; A.epsilon. = 5.7; Vth = 1.43 V; .eta. = 11.8 mPa
s; .gamma.1 = 62.1 mPa s.
TABLE-US-00009 Composition M6 3-GB(F,F)XB(F,F)-F (1-3) 5%
3-HGB(F,F)XB(F,F)-F (1-6) 5% 2-dhBB(F,F)XB(F,F)-F (1-8) 4%
3-dhB(F,F)B(F,F)XB(F)B(F,F)-F (1-13) 3% 3-HH-V (2) 26%
3-BB(2F,5F)B-3 (3) 3% 1V2-BB-1 (3-2) 3% 3-HB(F)HH-2 (3-8) 4%
5-HBB(F) B-2 (3-12) 6% 7-HB(F,F)-F (4-2) 3% 3-HGB(F,F)-F (4-6) 3%
5-GHB(F,F)-F (4-7) 4% 3-BB(F)B(F,F)-CF3 (4-13) 2% 3-HHBB(F,F)-F
(4-14) 4% 3-GBB(F)B(F,F)-F (4-16) 2% 2-HH-5 (--) 4% 2-HH-3 (--) 14%
1V2-HH-3 (--) 5% NI = 78.3.degree. C.; Tc < -20.degree. C.;
.DELTA.n = 0.094; .DELTA..epsilon. = 5.9; Vth = 1.25 V; .eta. =
12.8 mPa s; .gamma.1 = 61.9 mPa s.
TABLE-US-00010 Composition M7 3-BB(F)B(F,F)XB(F,F)-F (1-10) 3%
4-BB(F)B(F,F)XB(F,F)-F (1-10) 5% 3-BB(F,F)XB(F)B(F,F)-F (1-12) 3%
5-BB(F)B(F,F)XB(F)B(F,F)-F (1-14) 4% 3-HH-V (2) 25% 5-HB-O2 (3-1)
5% 7-HB-1 (3-1) 5% VFF-HHB-O1 (3-4) 8% VFF-HHB-1 (3-4) 3%
3-HBB(F,F)-F (4-8) 5% 5-HBB(F,F)-F (4-8) 4% 3-BB(F)B(F,F)-F (4-12)
3% 3-HH2BB(F,F)-F (4) 3% 4-HH2BB(F,F)-F (4) 3% 2-HH-5 (--) 8%
4-HH-V1 (--) 13% NI = 79.8.degree. C.; Tc < -20.degree. C.;
.DELTA.n = 0.101; .DELTA..epsilon. = 4.7; Vth = 1.71 V; .eta. =
11.1 mPa s; .gamma.1 = 47.8 mPa s.
TABLE-US-00011 Composition M8 3-BB(F,F)XB(F,F)-F (1-4) 10%
3-GB(F)B(F,F)XB(F,F)-F (1-9) 6% 5-GB(F,F)XB(F)B(F,F)-F (1-11) 5%
3-HH-V (2) 26% V2-BB-1 (3-2) 2% 5-HBBH-3 (3-10) 5% 5-HB(F)BH-3
(3-11) 5% 3-HHB(F,F)-F (4-4) 8% 3-GB(F)B(F,F)-F (4-11) 3% 3-HH-V1
(--) 14% 3-HH-VFF (--) 8% 1V2-HH-3 (--) 8% NI = 78.0.degree. C.; Tc
< -20.degree. C.; .DELTA.n = 0.089; .DELTA..epsilon. = 5.6; Vth
= 1.82 V; .eta. = 12.3 mPa s; .gamma.1 = 60.9 mPa s.
TABLE-US-00012 Composition M9 3-HHB(F,F)XB(F,F)-F (1-5) 5%
5-HHB(F,F)XB(F,F)-F (1-5) 3% 3-HGB(F,F)XB(F,F)-F (1-6) 5%
3-GB(F)B(F,F)XB(F,F)-F (1-9) 5% 4-GB(F)B(F,F)XB(F,F)-F (1-9) 5%
3-HH-V (2) 24% 3-HHEH-3 (3-3) 5% 5-B(F)BB-2 (3-7) 3% 5-B(F)BB-3
(3-7) 2% 5-HB-CL (4-1) 5% 3-HHB-OCF3 (4-3) 4% 3-HHEB(F,F)-F (4-5)
4% 3-HBEB(F,F)-F (4-10) 3% 5-HBEB(F,F)-F (4-10) 3% 3-BB(F)B(F,F)-F
(4-12) 3% 5-HEB(F,F)-F (4) 3% 3-HH-5 (--) 5% 2-HH-5 (--) 3%
1V2-HH-3 (--) 5% 4-HH-V (--) 5% NI = 78.6.degree. C.; Tc <
-20.degree. C.; .DELTA.n = 0.091; .DELTA..epsilon. = 6.8; Vth =
1.52 V; .eta. = 15.5 mPa s; .gamma.1 = 59.3 mPa s.
TABLE-US-00013 Composition M10 3-HHXB(F,F)-F (1-2) 9%
3-BB(F,F)XB(F,F)-F (1-4) 5% 3-HH-V (2) 25% 5-HB-O2 (3-1) 10% 7-HB-1
(3-1) 5% V2-BB-1 (3-2) 3% 3-HHB-1 (3-4) 4% 1V-HBB-2 (3-5) 5%
5-HBB(F)B-2 (3-12) 6% 3-HBB(F,F)-F (4-8) 3% 3-BB(F)B(F,F)-F (4-12)
4% 3-BB(F)B(F,F)-CF3 (4-13) 4% 3-GBB(F)B(F,F)-F (4-16) 3%
4-GBB(F)B(F,F)-F (4-16) 4% 3-HH-V1 (--) 10% NI = 79.6.degree. C.;
Tc < -20.degree. C.; .DELTA.n = 0.111; .DELTA..epsilon. = 4.7;
Vth = 1.86 V; .eta. = 9.7 mPa s; .gamma.1 = 49.9 mPa s.
TABLE-US-00014 Composition M11 3-BB(F,F)XB(F,F)-F (1-4) 14%
3-dhB(F,F)B(F,F)XB(F)B(F,F)-F (1-13) 7% 3-HH-V (2) 30%
3-BB(2F,5F)B-3 (3) 3% 3-HHB-O1 (3-4) 3% 3-HHB-1 (3-4) 4% 3-HHB-3
(3-4) 5% 3-HHEBH-3 (3-9) 3% 3-HHEBH-4 (3-9) 4% 3-HHEBH-5 (3-9) 3%
7-HB(F,F)-F (4-2) 6% 2-HH-5 (--) 5% 3-HH-V1 (--) 3% 3-HH-VFF (--)
10% NI = 82.7.degree. C.; Tc < -20.degree. C.; .DELTA.n = 0.085;
.DELTA..epsilon. = 5.1; Vth = 1.70 V; .eta. = 8.0 mPa s; .gamma.1 =
53.9 mPa s.
TABLE-US-00015 Composition M12 3-BB(F)B(F,F)XB(F,F)-F (1-10) 3%
4-BB(F)B(F,F)XB(F,F)-F (1-10) 5% 3-BB(F,F)XB(F)B(F,F)-F (1-12) 3%
5-BB(F)B(F,F)XB(F)B(F,F)-F (1-14) 4% 3-HH-V (2) 28% 5-HB-O2 (3-1)
2% 7-HB-1 (3-1) 5% VFF-HHB-O1 (3-4) 8% VFF-HHB-1 (3-4) 3%
3-HBB(F,F)-F (4-8) 5% 5-HBB(F,F)-F (4-8) 4% 3-BB(F)B(F,F)-F (4-12)
3% 3-HH2BB(F,F)-F (4) 3% 4-HH2BB(F,F)-F (4) 3% 2-BB(2F,3F)B-3
(5-11) 4% 3-HBB(2F,3F)-O2 (5-15) 2% 2-HH-5 (--) 8% 4-HH-V1 (--) 7%
NI = 81.9.degree. C.; Tc < -20.degree. C.; .DELTA.n = 0.109;
.DELTA..epsilon. = 4.8; Vth = 1.75 V; .eta. = 13.3 mPa s; .gamma.1
= 57.4 mPa s.
TABLE-US-00016 Composition M13 5-HHB(F,F)XB(F,F)-F (1-5) 3%
3-HGB(F,F)XB(F,F)-F (1-6) 4% 3-HBBXB(F,F)-F (1-7) 6%
3-GB(F)B(F,F)XB(F,F)-F (1-9) 5% 4-GB(F)B(F,F)XB(F,F)-F (1-9) 5%
3-HH-V (2) 21% 5-B(F)BB-2 (3-7) 3% 5-B(F)BB-3 (3-7) 2% 5-HB-CL
(4-1) 2% 3-HHB-OCF3 (4-3) 4% 3-HHEB(F,F)-F (4-5) 4% 3-HBEB(F,F)-F
(4-10) 3% 5-HBEB(F,F)-F (4-10) 3% 3-BB(F)B(F,F)-F (4-12) 3%
5-HEB(F,F)-F (4) 3% 3-HB(2F,3F)-O2 (5-1) 3% 3-BB(2F,3F)-O2 (5-5) 2%
3-HHB(2F,3F)-O2 (5-7) 4% 3-HH-5 (--) 4% 3-HH-V1 (--) 3% 1V2-HH-3
(--) 6% 4-HH-V (--) 4% F3-HH-V (--) 3% NI = 78.1.degree. C.; Tc
< -20.degree. C.; .DELTA.n = 0.100; .DELTA..epsilon. = 6.6; Vth
= 1.50 V; .eta. = 16.2 mPa s; .gamma.1 = 61.8 mPa s.
Polar compounds (PC-1) to (PC-33) described below were used as a
first additive.
##STR00065## ##STR00066## ##STR00067## ##STR00068##
Polymerizable compounds (RM-1) to (RM-11) described below were used
as a second additive.
##STR00069## ##STR00070##
2. Vertical Alignment of Liquid Crystal Molecules
Example 1
To composition (M1), polar compound (PC-1) was added at a
proportion of 5% by weight, and polymerizable compound (RM-1) was
added at a proportion of 0.5% by weight. The resulting mixture was
injected, on a hot stage at 100.degree. C., into a device having no
alignment film in which a distance (cell gap) between two glass
substrates was 4.0 micrometers. A polymerizable compound was
polymerized by irradiating the device with ultraviolet light (28J)
using an ultra-high pressure mercury lamp USH-250-BY (made by
Ushio, Inc.). The device was set to a polarizing microscope in
which a polarizer is arranged perpendicularly to an analyzer, and
the device is irradiated with light from below and presence or
absence of light leakage was observed. When liquid crystal
molecules were sufficiently aligned to prevent light from passing
through the device, vertical alignment was judged as "good." When
light that had passed through the device was observed, the vertical
alignment was represented as "poor."
Examples 2 to 33
A device having no alignment film was prepared by using a mixture
of a composition, a polar compound and a polymerizable compound.
Presence or absence of light leakage was observed in a manner
similar to Example 1. The results were summarized in Table 4.
TABLE-US-00017 TABLE 4 Vertical alignment of liquid crystal
molecules Polar Polymerizable Liquid compound compound crystal (5%
by (0.5% by Vertical Example composition weignt) weignt) alignment
1 M1 PC-1 RM-1 Good 2 M2 PC-2 RM-2 Good 3 M3 PC-3 RM-3 Good 4 M4
PC-4 RM-4 Good 5 M5 PC-5 RM-5 Good 6 M6 PC-6 RM-6 Good 7 M7 PC-7
RM-7 Good 8 M8 PC-8 RM-8 Good 9 M9 PC-9 RM-9 Good 10 M10 PC-10
RM-10 Good 11 M11 PC-11 RM-11 Good 12 M12 PC-12 RM-1 Good 13 M13
PC-13 RM-2 Good 14 M1 PC-14 RM-3 Good 15 M2 PC-15 RM-4 Good 16 M3
PC-16 RM-5 Good 17 M4 PC-17 RM-6 Good 18 M5 PC-18 RM-7 Good 19 M6
PC-19 RM-8 Good 20 M7 PC-20 RM-9 Good 21 M8 PC-21 RM-10 Good 22 M9
PC-22 RM-11 Good 23 M10 PC-23 RM-1 Good 24 M11 PC-24 RM-2 Good 25
M12 PC-25 RM-3 Good 26 M13 PC-26 RM-4 Good 27 M1 PC-27 RM-5 Good 28
M2 PC-28 RM-6 Good 29 M3 PC-29 RM-7 Good 30 M4 PC-30 RM-8 Good 31
M5 PC-31 RM-9 Good 32 M6 PC-32 RM-10 Good 33 M7 PC-33 RM-11
Good
The results shown in Table 4 indicate that the liquid crystal
molecules are stably aligned even without the alignment film by
using the liquid crystal composition containing the polar compound
and the polymerizable compound even though a kind of each component
is different. The above results are a noteworthy feature of the
invention.
INDUSTRIAL APPLICABILITY
According to a liquid crystal composition of the invention
alignment of liquid crystal molecules can be controlled in a device
having no alignment film. The liquid crystal composition satisfies
at least one of characteristics such as a high maximum temperature,
a low minimum temperature, small viscosity, suitable optical
anisotropy, large positive dielectric anisotropy, large specific
resistance, high stability to ultraviolet light, high stability to
heat and a large elastic constant, or has a suitable balance
regarding at least two of the characteristics. A liquid crystal
display device including the composition has characteristics such
as a short response time, a large voltage holding ratio, a low
threshold voltage, a large contrast ratio, a long service life and
so forth, and thus can be used in a liquid crystal projector, a
liquid crystal television and so forth.
* * * * *